Note: Descriptions are shown in the official language in which they were submitted.
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FABRIC CARE COMPOSITION
BACKGROUND OF THE INVENTION
Conventional fabric softening compositions are added in the rinse cycle of the
laundering
process to soften fabrics or as dryer added softener sheets to a machine
dryer. While various
softening compositions added in the rinse cycle are known, these compositions
lack in delivering
fully enough softening and/or other consumer desired benefits to the laundry.
While compositions exist that utilize coacervate phases such as softening
through the
wash (STW) compositions, it is believed that such phases may reduce the
overall softness feel
when attempting to use with conventional quaternary ammonium softening
compounds,
especially in rinse-added compositions. This reduction results in sub-optimal
results.
There is a need in the art to deliver an improved softening benefit to the
laundry.
Moreover, there is a need to deliver this improved need during the laundering
process. This
invention meets those needs.
SUMMARY OF THE INVENTION
In one aspect of the invention, there is a fabric enhancer composition
comprising: a. a
cationic polymer; b. less than about 20% silicone; c. a deposition aid;
wherein the composition is
essentially free of a coacervate.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, "deposition aids" are materials that enhance or enable the
deposition of
main fabric care materials on fabric article to provide the desired benefits.
The "deposition aids"
can be chemicals or compounds that are cationically modified by quaternized
amines thus carry
"permanent" cationic charge(s), or can potentially carry cationic charge(s) or
polarity in the use
medium through protonation of nitrogen atoms present in the compounds.
For purposes of the present invention the terms fabric enhancer and fabric
conditioner are
used interchangeably.
The term "fabric care" is used herein the broadest sense to include any
conditioning
benefit(s) to fabric. One such conditioning benefit includes softening fabric.
Other non-limiting
conditioning benefits include reduction of abrasion, reduction of wrinkles,
fabric feel, garment
shape retention, garment shape recovery, elasticity benefits, ease of ironing,
perfume, freshness,
color care, color maintenance, whiteness maintenance, increased whiteness and
brightness of
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fabrics, pilling reduction, static reduction, antibacterial properties, suds
reduction (especially in
high efficiency, horizontal axis washing machines), malodor control, or any
combination thereof.
One aspect of the invention provides fabric care compositions suitable for
dosing, for
example, into a washing machine. In one embodiment, a fabric enhancer
composition comprises:
a. a cationic polymer; b. less than about 20% silicone; and c. a deposition
aid wherein the
composition is essentially free of a coacervate.
While wishing not to be bound by theory, it is believed that while coacervates
are useful
for improving deposition of silicone, emulsions, perfume, and other materials;
in the present
invention, cationic surfactant (one example being cationic ammonium compounds)
is effectively
used to provide a softness feel to fabrics. To maintain compatibility (e.g.,
avoid precipitation)
between the fabric softener active and the deposition polymer, a cationic or
nonionic deposition
polymer is preferred. Typically, when using a cationic polymer, an anionic
surfactant is added to
form a coacervate phase. However, it is known to those skilled in the art that
addition of anionic
surfactant to a fabric softening composition comprising cationic surfactant
can compromise the
softening benefit. Thus, in one embodiment, anionic surfactant is excluded
from compositions of
the present invention.
A. Silicone
One aspect of invention comprises a fabric care composition comprising a
silicone as a
fabric care active. Silicone polymers, not only provide softness and
smoothness to fabrics, but
also provide a substantial color appearance benefit to fabrics, especially
after multiple laundry
washing cycles. While not wishing to be bound by theory, it is believed that
silicone polymers
provide an anti-abrasion benefit to fabrics in the washing or rinse cycles (or
both) of an automatic
washing machine by reducing friction of the fibers. Garments can look newer
longer and can last
longer before wearing out.
Levels of silicone will depend, in part, on whether the composition is
concentrated or
non-concentrated. Typical minimum levels of incorporation of silicone in the
present
compositions are at least about 0.1 Io, alternatively at least about 5 Io,
alternatively at least about
10%, and alternatively at least about 20%, by weight of the fabric care
composition; and the
typical maximum levels of incorporation of silicone are less than about 90%,
alternatively less
than about 70%, by weight of the fabric care composition.
In one embodiment, the composition is a concentrated composition comprising
from
about 5% to about 90%, alternatively from about 8% to about 70%, alternatively
about 9% to
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about 30%, alternatively from about 10% to 25%, alternatively from about 15%
to about 24%,
silicone by weight of the fabric care composition.
In another embodiment, the composition is a non-concentrated composition
comprising
from about 0.5% to about 30%, alternatively from about 2% to about 20%,
alternatively 4% to
about 10%, silicone by weight of the composition.
The silicone of the present invention can be any silicone comprising compound.
In one
embodiment, the silicone is a polydialkylsilicone, alternatively a
polydimethyl silicone
(polydimethyl siloxane or "PDMS"), or a derivative thereof. In another
embodiment, the silicone
is chosen from an aminofunctional silicone, alkyloxylated silicone,
ethoxylated silicone,
propoxylated silicone, ethoxylated/propoxylated silicone, quaternary silicone,
or combinations
thereof. Other useful silicone materials may include materials of the formula:
HO[Si(CH3)2-O]x{Si(OH)[(CH2)3-NH-(CH2)2-NH2]O}yH
wherein x and y are integers which depend on the molecular weight of the
silicone, preferably has
a molecular weight such that the silicone exhibits a viscosity of from about
500 cSt to about
500,000 cSt at 25 C. This material is also known as "amodimethicone".
Although silicones
with a high number of amine groups, e.g., greater than about 0.5 millimolar
equivalent of amine
groups can be used, they are not preferred because they can cause fabric
yellowing.
In one embodiment, the silicone is one comprising a relatively high molecular
weight. A
suitable way to describe the molecular weight of a silicone includes
describing its viscosity. A
high molecular weight silicone is one having a viscosity of from about 1,000
cSt to about
3,000,000 cSt, preferably from about 6,000 cSt to about 1,000,000 cSt,
alternatively about 7,000
cSt to about 1,000,000 cSt, alternatively 8,000 cSt to about 1,000,000 cSt,
alternatively from
about 10,000 cSt to about 600,000 cSt, alternatively from about 100,000 cSt to
about 350,000
cSt. In yet another embodiment, the silicone is a PDMS or derivatives thereof,
having a viscosity
from about 30,000 cSt to about 600,000 cSt, alternatively from about 75,000
cSt to about 350,000
cSt, and alternatively at least about 100,000 cSt. One example of a PDMS is DC
200 fluid from
Dow Corning. In yet another embodiment, the viscosity of the aminofunctional
silicone can be
low (e.g., from about 50 cSt to about 100,000 cSt).
For purposes of describing the present invention, any method can be used to
measure the
viscosity of the silicone. One suitable method is the "Cone/Plate Method" as
described herein.
The viscosity is measured by a cone/plate viscometer (such as Wells -
Brookfield cone/plate
viscometer by Brookfield Engineering Laboratories, Stoughton, MA.). Using the
Cone/Plate
Method, the spindle is "CP-52" and the revolutions per minute (rpm) is set at
5. The viscosity
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measurement is conducted at 25 C. Under the Cone/Plate Method, a typical PDMS
fluid
measured at about 100,000 cSt will have an average molecular weight of about
139,000. Without
wishing to be bound by theory, the high molecular weight silicone is more
viscous and is less
easily rinsed off of the fabrics in the washing and/or rinsing cycles of an
automatic washing
machine.
Another aspect of the invention provides a fabric care composition comprising
a silicone
emulsion. In one embodiment, the compositions of the present invention
comprise a first phase, a
second phase and an effective amount of an emulsifier such that the second
phase forms discrete
droplets in the continuous first phase. The second phase, or dispersed phase,
comprises at least
one fabric care active (such as a silicone). The dispersed phase may also
contain other fabric are
actives (such as, but not limited to, a static control agent and/or a
perfume). Additionally, the
first phase may also contain at least one fabric care active (such as a hueing
dye). Alternatively,
there may be several dispersed phases containing fabric care actives.
In one embodiment, if the fabric care active is a liquid, for example a
silicone liquid, the
second phase may form discrete droplets having a defined x50. In turn, ")~50"
is herein defined as
the median diameter of a particle (measured in micrometers) on a volumetric
basis. For example,
if the )~5o is 1000 m, then about 50% by volume of the particles are smaller
than this diameter
and about 50% are larger. In one embodiment, the droplets forming the second
phase have a )~5o
of less than about 1000 m, alternatively less than about 500 m,
alternatively less than about
100 m; alternatively at least about 0.1 m, alternatively at least about 1
m, alternatively at least
about 2 m, alternatively less than about 10 m. For purposes of describing
the present
invention, any method can be used to measure the )~5o of the droplets
comprising the second
phase, for example laser light scattering using a Horiba LA900 Particle Size
Analyzer. One
suitable method is described by the International Standard test method ISO
13320-1:1999(E) for
Particle Size Analysis - Laser Diffraction Methods.
While not wanting to be bound by theory, it is believed that silicone
particles smaller that
about 0.1 m are too fine to be effectively trapped in the fabrics during the
wash cycle and
silicone particles larger than about 1000 m provide poor distribution of
active on fabric,
resulting in less optimal benefits and even possible fabric spotting or
staining. In one
embodiment, the silicone particles from about 0.2 m to about 50 m. In on
embodiment, the
silicone particles from about 1 m to about 30 m in diameter. One aspect of
the invention
provides a fabric care composition comprising a PDMS and/or an aminofunctional
silicone. For
the aminofunctional silicone (also defined as "aminosilicone"), it is
preferred to have a viscosity
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of from about 50 cSt to about 1,500,000 cSt, preferably from about 100 cSt to
about 1,000,000
cSt, alternatively about 500 cSt to about 500,000 cSt, alternatively 1,000 cSt
to about 350,000
cSt, alternatively from about 1,500 cSt to about 100,000 cSt. In one
embodiment, the PDMS and
aminofunctional silicone are combined. It is preferred that the viscosity of a
combination of
PDMS and aminofunctional silicone be from about 500 cSt to about 100,000 cSt.
For example,
improved fabric care benefits may be achieved by combining the PDMS to
aminofunctional
silicone in a ratio from about 6:1 to about 1:3, alternatively from about 5:1
to about 1:1,
alternatively from about 4:1 to about 2:1, respectively. In another
embodiment, the PDMS to
aniinofunctional silicone ratio is combined in about 3:1 ratio before being
incorporated as part of
the fabric care composition.
One aspect of this invention is based upon the surprising discovery that high
molecular
weight PDMS, verses low molecular weight PDMS, may be more effective in
softening fabric.
However, high molecular weight PDMS is viscous and thus difficult to handle
from a processing
perspective. Adding the viscous PDMS and an emulsifier into the composition
can result in
inhomogeneous mixing of the ingredients. Surprisingly, by using a high
internal phase emulsion
("HIPE") as a premix, processing advantages are achieved. That is, by
premixing a silicone, such
as PDMS, and the emulsifier to create a HIPE, then mixing this HIPE into the
composition, good
mixing may be achieved thereby resulting in a homogeneous mixture. Net, a
composition that
exhibits good fabric benefits can be achieved.
HIPEs generally are comprised of at least about 65%, alternatively at least
about 70%,
alternatively at least about 74%, alternatively at least about 80%;
alternatively not greater than
about 95%, by weight of an internal phase (dispersed phase), wherein the
internal phase
comprises a silicone. The internal phase can also be other water insoluble
fabric care benefit
agents that are not already pre-emulsified. Pre-emulsified water insoluble
fabric care benefit
agents, for example, as discussed in the next section entitled "Other Water
Insoluble Fabric Care
Benefit Agents", can be used without the need to form a HIPE. The internal
phase is dispersed
by using an emulsifying agent. Examples of the emulsifying agent include a
surfactant or a
surface tension reducing polymer. In one embodiment, the range of the
emulsifying agent is from
at least about 0.1% to about 25%, alternatively from about 1% to about 10%,
and alternatively
from about 2% to about 6% by weight of the HIPE. In another embodiment, the
emulsifying
agent is water soluble and reduces the surface tension of water, at a
concentration less than of
0.1% by weight of deionized water, less than about 70 dynes, alternatively
less than about 60
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dynes, alternatively less than about 50 dynes; alternatively at or greater
than about 20 dynes. In
another embodiment, the emulsifying agent is at least partially water
insoluble.
The external phase (continuous phase), in one embodiment, is water,
alternatively
comprises at least some water, alternatively comprises little or no water. In
another embodiment,
the external phase of water comprises from less than about 35%, alternatively
less than about
30%, alternatively less than about 25%; alternatively at least about 1%, by
weight of HIPE. Non-
aqueous HIPEs can be prepared as well with a solvent as the external phase
with low or no water
present. Typical solvents include glycerin and propylene glycol. Other
solvents are listed in the
"Solvents" section of the present disclosure.
HIPEs are prepared by first combining the oil phase (internal phase) and the
emulsifying
agent. Then the external phase (e.g., water or solvent or a mixture thereof)
is added slowly with
moderate mixing to the combination of the oil phase and the emulsifying agent.
As a general
principle, the thinner (i.e., less viscous) the oil phase, the more important
it is to add the external
phase (e.g., water) slowly. At least one way to test the quality of the HIPE
is to simply add the
HIPE to water - if it readily disperses in water, then it is a good water
continuous HIPE. If the
HIPE does not disperse readily, then the HIPE may be improperly formed. When
making a HIPE
with a thick oil external phase, for example a PDMS at 100K cSt (100K cSt
means 100,000 cSt),
then it may be possible to mix the oil phase, emulsifying agent, and external
phase all together at
the same time and mix slowly by modest agitation. A HIPE may be easily formed
with this
procedure. An advantage to a HIPE, compared to a conventional emulsion, is
that a HIPE may
allow for processing with a relatively low amount of water. Such a low amount
of water may be
useful for unit dose executions of the present invention, wherein, for
example, fabric care
compositions are contained in a water soluble sachet comprised of polyvinyl
alcohol ("PVOH")
film. Such PVOH films generally require a relatively low level of water. In
one embodiment, the
concentrated fabric care composition comprises from about 0% to about 20%,
alternatively from
about 5 Io to about 15 Io, alternatively from about 8 Io to about 13 Io of
water by weight of the
fabric care composition.
In one embodiment, the composition is a highly concentrated composition. A
high
internal phase emulsion of silicone that is water continuous is prepared
before addition to the rest
of the formulation.
In another embodiment, the composition is a non-concentrated composition. In
this
embodiment, the silicone is not, at least initially, emulsified, i.e., the
silicone can be emulsified in
the fabric care composition itself.
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In yet another embodiment, the fabric care composition is free or essentially
free of a
silicone.
B. Other Water Insoluble Fabric Care Benefit A2ents
In addition to or in lieu of silicone, other materials can be used as well as
fabric care
benefit agents. Non-limiting examples of these other agents include: fatty
oils, fatty acids, soaps
of fatty acids, fatty triglycerides, fatty alcohols, fatty esters, fatty
amides, fatty amines; sucrose
esters, dispersible polyethylenes, polymer latexes, and clays.
Nonionic fabric care benefit agents can comprise sucrose esters, and are
typically derived
from sucrose and fatty acids. Sucrose ester is composed of a sucrose moiety
having one or more
of its hydroxyl groups esterified.
Sucrose is a disaccharide having the following formula:
/Fi
. il .:::.; . .',.. l': =1SJ r:
N;
Alternatively, the sucrose molecule can be represented by the formula: M(OH)8
, wherein
M is the disaccharide backbone and there are total of 8 hydroxyl groups in the
molecule.
Thus, sucrose esters can be represented by the following formula:
M(OH)8_X(OC(O)R')X
wherein x is the number of hydroxyl groups that are esterified, whereas (8-x)
is the
hydroxyl groups that remain unchanged; x is an integer selected from 1 to 8,
alternatively from 2
to 8, alternatively from 3 to 8, or from 4 to 8; and R' moieties are
independently selected from
C1-C22 alkyl or C1-C30 alkoxy, linear or branched, cyclic or acyclic,
saturated or unsaturated,
substituted or unsubstituted.
In one embodiment, the R' moieties comprise linear alkyl or alkoxy moieties
having
independently selected and varying chain length. For example, Rl may comprise
a mixture of
linear alkyl or alkoxy moieties wherein greater than about 20 Io of the linear
chains are C18,
alternatively greater than about 50% of the linear chains are C18,
alternatively greater than about
80% of the linear chains are C18.
In another embodiment, the R' moieties comprise a mixture of saturate and
unsaturated
alkyl or alkoxy moieties; the degree of unsaturation can be measured by
"Iodine Value"
(hereinafter referred as "IV", as measured by the standard AOCS method). The
IV of the sucrose
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esters suitable for use herein ranges from about 1 to about 150, or from about
2 to about 100, or
from about 5 to about 85. The R' moieties may be hydrogenated to reduce the
degree of
unsaturation. In the case where a higher IV is preferred, preferably from
about 40 to about 95,
then oleic acid and fatty acids derived from soybean oil and canola oil are
the preferred starting
materials.
In a further embodiment, the unsaturated R1 moieties may comprise a mixture of
"cis" and
"trans" forms about the unsaturated sites. The "cis" / "trans" ratios may
range from about 1:1 to
about 50:1, or from about 2:1 to about 40:1, or from about 3:1 to about 30:1,
or from about 4:1 to
about 20:1.
Non-limiting examples of water insoluble fabric care benefit agents include
dispersible
polyethylene and polymer latexes. These agents can be in the form of
emulsions, latexes,
dispersions, suspensions, and the like. Preferably they are in the form of an
emulsion or a latex.
Dispersible polyethylenes and polymer latexes can have a wide range of
particle size diameters
(xso ) including but not limited to from about 1 nm to about 100 um;
alternatively from about 10
nm to about 10 um. As such, the preferred particle sizes of dispersible
polyethylenes and
polymer latexes are generally, but without limitation, smaller than silicones
or other fatty oils.
Dispersible Polyolefins
Generally, all dispersible polyolefins that provide fabric care benefits can
be used as
water insoluble fabric care benefit agents in the present invention. The
polyolefins can be in the
format of waxes, emulsions, dispersions or suspensions. Non-limiting examples
are discussed
below.
In one embodiment, the polyolefin is chosen from a polyethylene,
polypropylene, or a
combination thereof. The polyolefin may be at least partially modified to
contain various
functional groups, such as carboxyl, alkylamide, sulfonic acid or amide
groups. In another
embodiment, the polyolefin is at least partially carboxyl modified or, in
other words, oxidized.
For ease of formulation, the dispersible polyolefin may be introduced as a
suspension or
an emulsion of polyolefin dispersed by use of an emulsifying agent. The
polyolefin suspension or
emulsion preferably compri ses from about 1 Io to about 60 Io, alternatively
from about 10 Io to
about 55%, alternatively from about 20% to about 50% by weight of polyolefin.
The polyolefin
preferably has a wax dropping point (see ASTM D3954- 94, volume 15.04 ---
"Standard Test
Method for Dropping Point of Waxes") from about 20 to about 170 C,
alternatively from about
50 to about 140 C. Suitable polyethylene waxes are available commercially
from suppliers
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including but not limited to Honeywell (A-C polyethylene), Clariant (Velustrol
emulsion), and
BASF (LUWAX ).
When an emulsion is employed with the dispersible polyolefin, the emulsifier
may be any
suitable emulsification agent. Non-limiting examples include an anionic,
cationic, nonionic
surfactant, or a combination thereof. However, almost any suitable surfactant
or suspending
agent may be employed as the emulsification agent. The dispersible polyolefin
is dispersed by
use of an emulsification agent in a ratio to polyolefin wax of about 1:100 to
about 1:2,
alternatively from about 1:50 to about 1:5, respectively.
Polymer Latexes
Polymer latex is made by an emulsion polymerization which includes one or more
monomers, one or more emulsifiers, an initiator, and other components familiar
to those of
ordinary skill in the art. Generally, all polymer latexes that provide fabric
care benefits can be
used as water insoluble fabric care benefit agents of the present invention.
Non-limiting
examples of suitable polymer latexes include those disclosed in WO 02/18451;
US
2004/0038851 Al; and US 2004/0065208 Al.. Additional non-limiting examples
include the
monomers used in producing polymer latexes such as: (1) 100 Io or pure
butylacrylate; (2)
butylacrylate and butadiene mixtures with at least 20% (weight monomer ratio)
of butylacrylate;
(3) butylacrylate and less than 20% (weight monomer ratio) of other monomers
excluding
butadiene; (4) alkylacrylate with an alkyl carbon chain at or greater than C6;
(5) alkylacrylate with
an alkyl carbon chain at or greater than C6 and less than 50% (weight monomer
ratio) of other
monomers; (6) a third monomer (less than 20% weight monomer ratio) added into
an
aforementioned monomer systems; and (7) combinations thereof.
Polymer latexes that are suitable fabric care benefit agents in the present
invention may
include those having a glass transition temperature of from about -120 C to
about 120 C,
alternatively from about -80 C to about 60 C. Suitable emulsifiers include
anionic, cationic,
nonionic and amphoteric surfactants. Suitable initiators include initiators
that are suitable for
emulsion polymerization of polymer latexes. The particle size diameter ()~5o)
of the polymer
latexes can be from about 1 nm to about 10 m, alternatively from about 10 nm
to about 1 m,
preferably from about 10 nm to about 20 nm.
In one embodiment, the fabric care composition of the present invention is
free or
essentially free of other water insoluble fabric care benefit agents.
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C. Coacervate Phase
One aspect of this invention provides for a composition essentially free of a
coacervate
phase. A coacervate is typically an interaction product of a cationic polymer
or cationic
surfactant and an anionic surfactant. The level of the coacervate in the
compositions of the
present invention are from about 0.0001 Io to about 1 Io, alternatively from
about 0.0001 Io to
about .005%, and alternatively about 0% by weight of the fabric care
composition.
D. Cationic Polymers
The term "cationic polymer" is used herein the broadest sense to include any
polymer
(including, in one embodiment, a cationic surfactant) which has a cationic
charge. Some cationic
polymers can function as deposition aids as described in the next section; or
alternatively, provide
fabric care benefits on their own such as antiabrasion effects to improve the
appearance of
colored fabrics.
The fabric care compositions herein can contain from about 0.001% to about
10%,
alternatively from about 0.01 Io to about 5 Io, alternatively from about 0.1
Io to about 2%, of
cationic polymer, typically having a molecular weight of from about 500 to
about 5,000,000
(although some cationic starches can be as high as 10,000,000 in molecular
weight), alternatively
from about 1,000 to about 2,000,000, alternatively from about 1,000 to about
1,000,000, and
alternatively from about 2,000 to about 500,000 and a charge density of at
least about 0.01
meq/gm., and up to about 23 meq/gm., alternatively from about 0.05 to about 8
meq/gm.,
alternatively from about 0.08 to about 7 meq/gm., and even alternatively from
about 0.1 to about
1 milliequivalents/gram (meq/gm).
The cationic polymers of the present invention can be amine salts or
quaternary ammonium
salts. Preferred are quaternary ammonium salts. They include cationic
derivatives of natural
polymers such as some polysaccharide, gums, starch and certain cationic
synthetic polymers such
as polymers and copolymers of cationic vinyl pyridine or vinyl pyridinium
halides. Preferably the
polymers are water-soluble, for instance to the extent of at least 0.5% by
weight are soluble in
water at 20 C. Preferably the polymers have molecular weights (Daltons) of
from about 500 to
about 5,000,000, preferably from about 1,000 to about 2,000,000, more
preferably from about
1,000 to about 1,000,000, and even more preferably from about 2,000 to about
500,000, and
especially from about 2000 to about 100,000. As a general rule, the lower the
molecular weight,
the higher the degree of substitution (D.S.) by cationic, usually quaternary
groups, which is
desirable, or, correspondingly, the lower the degree of substitution, the
higher the molecular weight
which is desirable, but no precise relationship appears to exist. In general,
the cationic polymers
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may have a charge density of at least about 0.01 meq/gm., preferably from
about 0.05 to about 8
meq/gm., more preferably from about 0.08 to about 7 meq/gm., and even more
preferably from
about 0.1 to about 1 meq/gm. Cationic polymers are disclosed in U.S. Patent
No. 6,492,322 at
column 6, line 65 to colunm 24, line 24. Other cationic polymers are disclosed
in the CTFA
"International Cosmetic Ingredient Dictionary and Handbook," Tenth Edition,
Tara E. Gottschalck
and Gerald N. McEwen, Jr., editors, published by The Cosmetic, Toiletry, and
Fragrance
Association, 2004. Still other cationic polymers are described at U.S. Patent
Publication 2003-
0139312 Al, published July 24, 2003, from paragraph 317 to paragraph 347. The
list of the
cationic polymers includes the following.
In one embodiment, the cationic polymer comprises a polysaccharide gum. Of the
polysaccharide gums, guar and locust bean gums, which are galactomannam gums
are available
commercially, and are preferred. In another embodiment, the cationic polymer
comprises cationic
guar gum. Guar gums are marketed under Trade Names CSAA M/200, CSA 200/50 by
Meyhall
and Stein-Hall, and hydroxyalkylated guar gums are available from the same
suppliers. Other
polysaccharide gums commercially available include: Xanthan Gum; Ghatti Gum;
Tamarind
Gum; Gum Arabic; and Agar. Cationic guar gums under the Trade Name N-Hance are
available
from Aqualon.
Suitable cationic starches and derivatives are the natural starches such as
those obtained
from maize, wheat, barley etc., and from roots such as potato, tapioca etc.,
and dextrins,
particularly the pyrodextrins such as British gum and white dextrin.
Some preferred individual cationic polymers are the following: Polyvinyl
pyridine,
molecular weight about 40,000, with about 60% of the available pyridine
nitrogens quaternized;
copolymer of 70/30 molar proportions of vinyl pyridine/styrene, molecular
weight about 43,000,
with about 45% of the available pyridine nitrogens quaternized as above;
copolymers of 60/40
molar proportions of vinyl pyridine/acrylamide, with about 35% of the
available pyridine nitrogens
quaternized as above; copolymers of 77/23 and 57/43 molar proportions of vinyl
pyridine/methyl
methacrylate, molecular weight about 43,000, with about 97% of the available
pyridine nitrogens
quaternized as above. These cationic polymers are effective in the
compositions at very low
concentrations for instance from 0.001 Io by weight to 0.2% especially from
about 0.02% to 0.1 Io
by weight of the fabric care composition.
Some other cationic polymers include: copolymer of vinyl pyridine and N-vinyl
pyrrolidone (63/37) with about 40% of the available pyridine nitrogens
quaternized; copolymer of
vinyl pyridine and acrylonitrile (60/40), quaternized as above; copolymer of
N,N-dimethyl amino
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ethyl methacrylate and styrene (55/45) quaternized as above at about 75% of
the available amino
nitrogen atoms; and Eudragit ETM (Rohm GmbH) quaternized as above at about 75%
of the
available amino nitrogens. Eudragit ETM is believed to be copolymer of N,N-
dialkyl amino alkyl
methacrylate and a neutral acrylic acid ester, and to have molecular weight
about 100,000 to
1,000,000. Another example of a cationic polymer includes a copolymer of N-
vinyl pyrrolidone
and N,N-diethyl amino methyl methacrylate (40/50), quaternized at about 50% of
the available
amino nitrogens. These cationic polymers can be prepared in a known manner by
quaternizing
the basic polymers.
Other useful cationic polymer examples include Magnafloc 370 (from Ciba
Specialty
Chemicals) also know by the CTFA name as Polyquaternium-6, as well as
Polyquaternium-10
and Polyquaternium-24 (from Amerchol Corporation), and polyvinylamine also
known as
Lupamin (e.g., Lupamin 1595 and Lupamin 5095 from BASF). Magnafloc 370 has a
relatively
high charge density of about 6 meq/g. Lupamins can have molecular weights from
about 10,000
to about 20,000 and a very high charge density of about 23 meq/g. Other
examples of cationic
polymers are chitosan, oligochitosan (preferred are materials with a molecular
weight from about
500 to about 2,000,000, more preferably from about 500 to about 50,000; a
degree of acetylation
of from about 70% and lower; and a polydispersity of from about 0 to about 10,
preferably from
about 1 to about 3), chitosan derivatives, quaternized chitosan, and Syntahlen
CR
(Polyquaternium-37) available from 3V.
Further examples of cationic polymers include cationic polymeric salts such as
quaternized
polyethyleneimines. These have at least 10 repeating units, some or all being
quaternized.
Commercial examples of polymers of this class are also sold under the generic
Trade Name
AlcostatTM by Allied Colloids. Typical examples of cationic polymers are
disclosed in U.S. Pat.
No. 4,179,382 to Rudkin, et. al., column 5, line 23 through column 11, line
10. Each polyamine
nitrogen whether primary, secondary or tertiary, is further defined as being a
member of one of
three general classes; simple substituted, quaternized or oxidized. The
polymers are made neutral
by water-soluble anions such as chlorine (Cl-), bromine (Br ), iodine (I-) or
any other negatively
charged radical such as sulfate (S042-) and methosulfate (CH3S03-). Specific
polyamine
backbones are disclosed in U.S. Pat. Nos. 2,182,306; 3,033,746; 2,208,095;
2,806,839;
2,553,696. An example of modified polyamine cationic polymers of the present
invention
comprising PEI's comprising a PEI backbone wherein all substitutable nitrogens
are modified by
replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2O)7H. Other
suitable
polyamine cationic polymers comprise this molecule which is then modified by
subsequent
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oxidation of all oxidizable primary and secondary nitrogens to N-oxides and/or
some backbone
amine units are quaternized, e.g. with methyl groups.
Preferred cationic polymers include cationic guar gums and cationic cellulose
polymers.
The preferred cationic guar gums include the N-Hance 3000 series from Aqualon
(N-Hance
3000, 3196, 3198, 3205, and 3215). These have a range of charge densities from
about 0.07 to
about 0.95 meq/gm. Another effective cationic guar gum is Jaguar C-13S.
Cationic guar gums are
a highly preferred group of cationic polymers in compositions according to the
present invention
and act both as scavengers for residual anionic surfactant (if used in the
rinse cycle) and also add to
the softening effect of cationic textile softeners even when used in baths
containing little or no
residual anionic surfactant. The other polysaccharide-based gums can be
quaternized similarly and
act substantially in the same way with varying degrees of effectiveness.
Cationic guar gums and
methods for making them are disclosed in British Pat. No. 1,136,842 and U.S.
Pat. No. 4,031,307.
Preferably cationic guar gums have a D.S. of from about 0.1 to about 0.5.
Some highly preferred cationic guar gums and their physical properties are
shown below:
Cationic Polymer Supplier MW Viscosity De2ree of
Substitution
Meypro-Coat 21 Rhodia 50K 100 (3 Io) 0.1
N-Hance 3269 Aqualon 500K 25-65 (1 Io) 0.13
Jaguar Exel Rhodia na 500 (1 Io) 0.1
N-Hance 3000 Aqualon 1200K 1000-2000 (1%) 0.07
N-Hance 3196 Aqualon 1600K 4000-5000 (1%) 0.13
Jaguar C-13S Rhodia 2000K 3000 (1 Io) 0.13
Jaguar C-17 Rhodia 2000K 3000 (1 Io) 0.17
N-Hance 3215 Aqualon 1500K 3200-4200 (1%) 0.20
Cationic hydroxypropyl guars can also be use as cationic deposition aids, but
may give
somewhat lower performance. Useful examples include Jaguar C-162 and Jaguar C-
2000 (ex.
Rhodia).
Cationic cellulose polymers can also be used and another preferred class of
materials.
Included are "amphoteric" polymers of the present invention since they will
also have a net
cationic charge, i.e.; the total cationic charges on these polymers will
exceed the total anionic
charge. The degree of substitution of the cationic charge can be in the range
of from about 0.01
(one cationic charge per 100 polymer repeating units) to about 1.00 (one
cationic charge on every
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polymer repeating unit) and preferably from about 0.01 to about 0.20. The
positive charges could
be on the backbone of the polymers or the side chains of polymers.
While there are many ways to calculate the charge density of cationic
celluloses, the
degree of substitution of the cationic charge can be simply calculated by the
cationic charges per
100 glucose repeating units. One cationic charge per 100 glucose repeating
units equals to 1%
charge density of the cationic celluloses.
Preferred cationic celluloses for use herein include those which may or may
not be
hydrophobically-modified, having a molecular weight (Dalton) of from about
50,000 to about
2,000,000, more preferably from about 100,000 to about 1,000,000, and most
preferably from
about 200,000 to about 800,000. These cationic materials have repeating
substituted
anhydroglucose units that correspond to the general Structural Formula I as
follows:
O Rl
O
O
R30 O R2
RA
(I)
wherein Rl, R2, R3 are each independently H, CH3, C8_24 alkyl (linear or
branched),
R5
1
~CH2CH-O I Rx
or mixtures thereof; wherein n is from about 1 to about 10; Rx is H, CH3, C8_
OH R7
-CHzCHCHz-N R9 Z
18
24 alkyl (linear or branched), R or mixtures thereof, wherein Z is a water
soluble anion, preferably a chlorine ion and/or a bromine ion; R5 is H, CH3,
CH2CH3, or mixtures
thereof; R7 is CH3, CH2CH3, a phenyl group, a C8_24 alkyl group (linear or
branched), or mixture
thereof; and
R8 and R9 are each independently CH3, CH2CH3, phenyl, or mixtures thereof:
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tP~H
R4 is H, m, or mixtures thereof wherein P is a repeat unit of an addition
polymer formed
by radical polymerization of a cationic monomer such as
CH~ CH3
z +~~
q
q
wherein Z' is a water-soluble anion, preferably chlorine ion, bromine ion or
mixtures thereof and
q is from about 1 to about 10.
The charge density of the cationic celluloses herein (as defined by the number
of cationic
charges per 100 glucose units) is preferably from about 0.5 % to about 60%,
more preferably
from about 1% to about 20%, and most preferably from about 2% to about 10%.
Alkyl substitution on the anhydroglucose rings of the polymer ranges from
about 0.01 Io to
about 5% per glucose unit, more preferably from about 0.05% to about 2% per
glucose unit, of
the polymeric material.
The cationic cellulose ethers of Structural Formula I likewise include those
which are
commercially available and further include materials which can be prepared by
conventional
chemical modification of commercially available materials. Commercially
available cellulose
ethers of the Structural Formula I type include the JR 30M, JR 400, JR 125, LR
400 and LK 400
polymers, all of which are marketed by Dow Chemical.
Another example of a cationic polymer is a cationic polysaccharide, preferably
starch,
compound. The terms "polysaccharide" and "cationic starch" are used herein in
the broadest
sense. A cationic starch can also be used as a fabric care active, e.g., for
softness and
conditioning. Cationic starches are described in U.S. Pat. Pub. 2004/0204337
Al.
In one embodiment, the fabric care composition is free or essentially free of
a cationic
polymer.
E. Deposition Aid
The fabric care composition may also comprise deposition aids including, but
not limited to 1)
non-quaternary materials that are (a) acyclic polymers or copolymers having
nitrogen moieties in the
backbone or in the pendant groups, or (b) vinyl polymers or copolymers having
nitrogen heterocyclics in
the pendant groups; II) non-polysaccharide polyquaterniums and other polymeric
cationic quaternary
materials; and mixtures thereof. The deposition aid improves the deposition of
a fabric care active with
some examples being silicone or other insoluble actives.
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The deposition aids suitable for use herein are polymeric materials having a
weight average
molecular weight generally in the range from about 1000 to about 1,000,000, or
from about 1000 to about
200,000, or from about 2500 to about 1,000,000, or from about 5000 to about
500,000. In some
embodiments, the deposition aid is polyacrylamide or derivatives thereof, the
weight average molecular
weight of the deposition aid is from about 1,000,000 to about 15,000,000.
When present, each deposition aid comprises, based on total composition
weight, at one
of the following levels, from about 0.1% to about 20%, preferably from about
0.2% to about
15%, more preferably from about 0.2% to about 10 wt %, and most preferably
from about 0.2%
to about 5 Io.
In some embodiments of the present invention, suitable deposition aids are
acyclic polymers or
copolymers derived from monomers having nitrogen moieties, including but not
limited to, amine, imine,
amide, imide, acrylamide, methacrylamide, amino acid, and mixtures thereof.
Nonlimiting examples of
suitable deposition aids are described below:
Acyclic Polymers or Copolymers Having Nitrogen Moieties
a) Polyvinylamine (PVAm)
NH2
Examples of this polymeric material are available as Catiofast PR8085,
PR8106, PR8134,
Lupamin all of which are from BASF and are typically used as cross-linking
agents or
flocculating agents in paper-making industry.
b) Polyethyleneimine (PEI)
N..,/'N
; HN
I I Pd
~,..,,.^..N or
'=~~=i^.=.
Fi n f~ J.
F~'~. N _~ H
~
PH
Examples of this polymeric material are available as Lupasol and Polymin
from BASF, or as
Catiofast PL, SF, GM, PR8138, all of which are from BASF and are typically
used as cross-
linking agents or flocculating agents in paper-making industry.
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c) Grafted and Crosslinked PolyAmido-Polyethyleneimine
NHZ HN-'-)
O
~ ~ NHZ
NN-`~ N^/~N
H n
O
N
NHZ
H2N
d) Ethoxylated Polyethyleneimine (PEI-E)
H ~
T
O O'~xH
~ ~,\L,,~F^+.,\I.
x
O o~xH x
I,I,In or H~ --x
N'ti ,, rI Nh \!'\ , ., x L J ~
H ~ x ,'~ ~ 0 x O~' x
H
H
wherein, x = 1-40
e) Polyacrylamide
O NH2
f) Poly(2-dimethylaminoethyl methacrylate)
CH,
-H2C-~_
I -O I C H3
O-CH2CH2-N-CH3
g) Poly(amino acids): for example, polylysine would have the following
formula:
O
H
N
NH2
additional examples of poly(amino acids) are selected from the group
consisting of:
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(1) homo-condensates of basic amino acids, said amino acids selected from the
group consisting of
lysine, ornithine, arginine, and tryptophan;
(2) co-condensates of basic amino acids, said amino acids selected from the
group consisting of
lysine, ornithine, arginine, and tryptophan;
(3) co-polymers produced from the reaction of one or more basic amino acids
with one or more
co-condensable compounds;
(4) co-polymers produced from the reaction of one or more homo-condensates
from (1) or co-
condensates from (2) with one or more co-condensable compounds;
(5) crosslinked basic amino acid-containing polymers, said crosslinked
polymers comprising:
i) one or more basic amino acids;
ii) co-polymers of (i) and one or more co-condensable compounds;
iii) optionally co-polymers produced from the reaction of one or more homo-
condensates
from (1) or co-condensates from (2) with one or more co-condensable compounds;
and
iv) one or more crosslinking unit;
wherein at least one crosslinking unit is derived from a crosslinker which
comprises at least two
functional groups;
(6) co-condensates formed from the reaction of one or more compounds selected
from the group
consisting of:
i) basic amino acids;
ii) co-condensable compounds;
iii) crosslinking agents; and
(7) mixtures thereof.
h) Polylysine Aminocaproic Acid Derivatives
0 X = # of Caproic unit
HO N R Y = # of Lysine unit
-+Ir,,_,,,_H J~~~_H N Z = # Acid unit
X y ~
O NH2 O R: CH3 (Acetic)
CH2CH3 (Propionic)
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Vinyl Polymers or Copolymers Having Nitrogen Heterocyclic Pendant Moieties
In some embodiments of the present invention, suitable deposition aids are
vinyl polymers or
copolymers derived from vinyl monomers having nitrogen heterocyclic pendant
moieties having the
formula:
R1 R2
1 1
C-C
R1 Z
wherein R', R2 are independently hydrogen, halogen, linear or cyclic,
saturated or unsaturated C1-C4
alky or alkoxy, substituted or unsubstituted phenyl, benzyl, naphthayl or
hetrocyclics, and mixtures
thereof; Z is nitrogen heterocyclics, including nitrogen heterocyclic N-
oxides.
Nonlimiting examples of these deposition aids are described below:
a) Polyvinylpyrrolidone (PVP)
b) Polyvinylpyridine
~ I ~ IN
\N \
c) Polyvinylpyridine-N-oxide (PVNO)
N
I I
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d) Polyvinylpyrrolidone Vinyl Imadazole (PVPVI)
x y
N 0 N
N
e) Copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate
CH3
x '-ty i H3
N O ~ /N
O" CH3
Non-polysaccharide Polyquaterniums and Other Polymeric Cationic Quaternary
Materials
In some embodiments of the present invention, suitable deposition aids are non-
polysaccharide
polyquaterniums, other polymeric catoinic quaternary materials or mixtures
thereof. As used herein, the
term "polyquaternium-x" has the same meaning as that of INCI (International
Nomenclature Cosmetic
Ingredient). These cationic quaternary materials can be paired with anions,
including but not limited to
halogen or S03CH3. Nonlimiting examples of these deposition aids are described
below:
a) Polyquaternium-2:
~ H3 0 CH3
N+-CH2CH2CH2NHCNHCH2CHCH3-N+-CH2CH2OCH2CH2
I Cl- I Cl-
CH3 CH3
Examples of this polymeric material are available as Mirapol A-15 (from
Rhodia)
b) Polyquaternium-6: N,N-Dimethyl-N-2-propen-l-ammonium chloride homopolymer
(PDADMAC)
*
*
n
N+ CI-
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Examples of this polymeric material are available as Merquat 100 (from
Nalco), Percol 370 or
Magnafloc 370 (from CIBA)
c) Polyquaternium-7: Copolymer of acrylamide and N,N-Dimethyl-N-2-propen-l-
ammonium
chloride
H
H2C-C
C=0
NH2
/N+ \1 Cl-
Examples of this polymeric material are available as Merquat 550 (from Nalco)
or Mirapol 550
(from Rhodia)
d) Polyquaternium-11: Quaternized Poly(vinylpyrrolidone/Dimethylaminoethyl
Acrylate
H2C- i H2C- i
CH3
ON O-CH2CH2N*-CH3
=0 CH3 C2H5S03Examples of this polymeric materia1areavailable as Gafquat 755,
755N, 734 (from ISP)
e) Polyquaternium-16: Copolymer of Polyvinylpyrrolidone and imidazolinium
methochloride
H2C-CH2C-C
\ 0 N-O ON CI-
\CH3
Examples of this polymeric material are available as Luviquat FC and Luviquat
HM (from
BASF).
f) Polyquaternium-17: examples of this polymeric material are available as
Mirapol AD-1 (from
Rhodia)
I CH, CH3
N'-CHCH2CH2NHC(CH2)4CNHCH2CHCH3-N'-CH2CH2OCH2CH2
I Cr I Cl-
CH3 CH3
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g) Polyquaternium-18: examples of this polymeric material are available as
Mirapol AZ-1 (from
Rhodia)
I
CH3 I1 11 CH3
H3
N*-CHCHZCHZNHC(CHZ)7CNHCHZCHCH3-N*-CHZCHZOCHZCHZ
I ci- I ci-
CH3 CH3
h) Polyquaternium-22: Copolymer of sodium acrylate and dimethyl diallyl
ammonium chloride
H
H2C-C
C
O- Na'
N' Cl-
Examples of this polymeric material are available as Merquat 280 and 295
(Nalco).
i) Polyquaternium-28: Copolymer of vinylpyrrolidone and methacrylate
amidopropyl/trimethylammonium Chloride
H iCH3
HZC-C HZC-C
i =0 C=0 CH3
HN-CCHZCHZ-N*-CH3
GN=O CH3 CIExamples of thispolymeric material are available as Gafquat HS-100
(ISP)
j) Cationic polyacrylamide such as polyacrylamide ethyl trimethylammonium
cation
X y CH3
CH3
O NH2 O N'
O" C\CH3
Examples of this polymeric material are available as Sedipur CF (from BASF)
wherein the cation
is paired with a chloride anion.
k) Poly(2-acryloyloxyethyl)trimethylammonium cation, which may be paired with
anion such as
methylsulfate.
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H
H2C- i
I -O Ci H3
O-CH2CH2 N+-CH3
CH3 OSO3CH3
1) Polymethacrylamidopropyl trimethylammonium cation
iH3
, LH2C- i -,
L I -O CH3
NH-CH2CH2CH2-N+-CH3
CH3 C1
Examples of this polymeric material are available as Polycare 133 (from
Rhodia), wherein the
cation is paired with a chloride anion.
m) Copolymers which contain polyamide, polyether and polyethylenimine, such
as:
ty N~\NN
O
+NH/~N.N7
O NH2
Examples of this polymeric material are available as Polymin from BASF.
Additional
F. Emulsifyim and Disuersin2 A2ents
The compositions of the present invention may contain a dispersing agent or an
emulsifying agent to (1) form a conventional silicone emulsion or a high
internal phase emulsion
("HIPE") silicone emulsion and/or (2) help disperse the composition.
Other useful surfactants may include nonionics, cationics, zwitterionics,
ampholytic
surfactants, and mixtures thereof. These surfactants are emulsifers for the
silicone and may also
help disperse the composition in the wash cycle. In an alternative embodiment,
the HIPE or
silicone emulsion is free or substantially free of any one or more of these
surfactants. In one
embodiment, the fabric care compositions are essentially free of anionic
surfactants.
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Nonionic Surfactants
Suitable nonionic surfactants useful herein for either emulsification of the
silicone
polymer or dispersing the composition in the wash (or both) can comprise any
of the
conventional nonionic surfactant types typically used in liquid and/or solid
detergent products.
These include alkoxylated fatty alcohols and amine oxide surfactants.
Suitable nonionic surfactants for use herein include the alcohol alkoxylate
nonionic
surfactants. Alcohol alkoxylates are materials which correspond to the general
formula:
Ri(CmH2mO)õOH wherein R' is a C8 - C16 alkyl group, m is from 2 to 4, and n
ranges from about
2 to 12. Preferably R' is an alkyl group, which may be primary or secondary,
that contains from
about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
In one
embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials
that contain from
about 2 to 12 ethylene oxide moieties per molecule, more preferably from about
3 to 10 ethylene
oxide moieties per molecule.
The alkoxylated fatty alcohol materials useful in the detergent compositions
herein will
frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about
3 to 17. More
preferably, the HLB of this material will range from about 6 to 15, most
preferably from about 8
to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under
the tradenames
Neodol and Dobanol by the Shell Chemical Company.
Another suitable type of nonionic surfactant useful herein comprises the amine
oxide
surfactants. Amine oxides are materials which are often referred to in the art
as "semi-polar"
nonionics. Amine oxides have the formula:
R(EO)X(PO)y(BO)zN(O)(CH2R')2.qH2O.
In this formula, R is a relatively long-chain hydrocarbyl moiety which can be
saturated or
unsaturated, linear or branched, and can contain from 8 to 20, preferably from
10 to 16 carbon
atoms, and is more preferably C12-C16 primary alkyl. R' is a short-chain
moiety, preferably
selected from hydrogen, methyl and -CHZOH. When x+y+z is different from 0, EO
is
ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide
surfactants are
illustrated by C12_14 alkyldimethyl amine oxide.
Non-limiting examples of nonionic surfactants include: a) C12-C18 alkyl
ethoxylates, such
as, NEODOL nonionic surfactants from Shell; b) C6-C12 alkyl phenol
alkoxylates wherein the
alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-
C18 alcohol and C6-
C12 alkyl phenol condensates with ethylene oxide/propylene oxide block
polymers such as
Pluronic from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed
in US
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6,150,322; e) C14-C22 mid-chain branched alkyl alkoxylates, BAEX, wherein x 1-
30, as discussed
in US 6,153,577, US 6,020,303 and US 6,093,856; f) Alkylpolysaccharides as
discussed in U.S.
4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides
as discussed in US
4,483,780 and US 4,483,779; g) Polyhydroxy fatty acid amides as discussed in
US 5,332,528,
WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped
poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO
01/42408.
Other preferred nonionic surfactants include Planteran 2000, Laureth-7 and
Lonza PGE-
10-1-L, Neodo123-9, and Neodo125-3, or mixtures thereof.
Cationic Surfactants
Cationic surfactants are well known in the art and non-limiting examples of
these include
quaternary ammonium surfactants, which can have up to 26 carbon atoms.
Additional examples
include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in US
6,136,769; b)
dimethyl hydroxyethyl quaternary ammonium as discussed in 6,004,922; c)
polyamine cationic
surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO
98/35005, and WO
98/35006; d) cationic ester surfactants as discussed in US Pat. Nos.
4,228,042, 4,239,660
4,260,529 and 6,022,844; and e) amino surfactants as discussed in US 6,221,825
and WO
00/47708, specifically amido propyldimethyl amine (APA); f) combinations
thereof.
Zwitterionic Surfactants
Non-limiting examples of zwitterionic surfactants include: derivatives of
secondary and tertiary
amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of quaternary
ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S.
Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at colunm 19, line 38
through column 22,
line 48, for examples of zwitterionic surfactants; betaine, specific examples
include alkyl
dimethyl betaine and cocodimethyl amidopropyl betaine, C8 to C18 (preferably
C12 to C18) amine
oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino- 1 -
propane
sulfonate where the alkyl group can be C8 to C18, preferably Cio to C14.
Ampholytic Surfactants
Non-limiting examples of ampholytic surfactants include: aliphatic derivatives
of
secondary or tertiary amines, or aliphatic derivatives of heterocyclic
secondary and tertiary
amines in which the aliphatic radical can be straight- or branched-chain. One
of the aliphatic
substituents contains at least about 8 carbon atoms, typically from about 8 to
about 18 carbon
atoms, and at least one contains an anionic water-solubilizing group, e.g.
carboxy, sulfonate,
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26
sulfate. See U.S. Patent No. 3,929,678 at col. 19, lines 18-35, for examples
of ampholytic
surfactants.
G. Static Control Aunts
One aspect of the invention provides for a composition of present invention
comprising a
static control agent. In one embodiment, the static control agent comprises
ion-pair conditioning
particles. In turn, these particles may comprise water-insoluble particles
comprised of certain
amine-organic anion ion-pair complexes and, optionally, certain amine-
inorganic anion ion-pair
complexes. The primary benefit of these conditioning particles in the present
invention is to
provide antistatic benefits to fabrics, especially those fabrics dried in a
machine dryer. These
complexes and other non-complexed materials that provide static control are
hereafter called
Static Control Agents (SCAs).
Although these complexes provide antistatic benefits to laundry, a problem
posed by the
use of these ingredients includes incompatibility with use of a perfume. Thus
one aspect of the
invention is based upon the surprising discovery of separating perfume and
these ion-pair
complexes before these compositions are administered during the laundry
process.
The amine-organic anion ion-pair complexes can be represented by the following
formula:
R1
I -
R2 i+ R3 A
H
wherein each Rl and R2 can independently be C12 to C20 alkyl or alkenyl, and
each R3 is H or
CH3. A represents an organic anion and includes a variety of anions derived
from anionic
surfactants, as well as related shorter alkyl or alkenyl chain compounds which
need not exhibit
surface activity. A is selected from the group consisting of alkyl sulfonates,
aryl sulfonates,
alkylaryl sulfonates, alkyl sulfates, dialkyl sulfosuccinates, alkyl
oxybenzene sulfonates, acyl
isethionates, acylalkyl taurates, alkyl ethoxylated sulfates, and olefin
sulfonates, and mixtures of
such anions. A preferred starting material for "A" is cumene sulfonic acid.
As used herein the term alkyl sulfonate shall include those alkyl compounds
having a
sulfonate moiety at a fixed or predetermined location along the carbon chain,
as well as
compounds having a sulfonate moiety at a random position along the carbon
chain.
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27
The optionally incorporated amine-inorganic anion ion-pair complexes can be
represented
by the following formula:
R1
R2 I + R3 BX
X
wherein each Rl and R2 can independently be C12 to C20 alkyl or alkenyl, each
R3 is H or CH3,
and x corresponds to the molar ratio of the amine to the inorganic anion and
the valence of the
inorganic anion, x being an integer between 1 and 3, inclusive. B is an
inorganic anion such as,
but not limited to, sulfate (S04 2), hydrogen sulfate (HS041), nitrate (N03-),
phosphate (P04 3)
hydrogen phosphate (HP04 Z), and dihydrogen phosphate (H2 P04-1), and mixtures
thereof,
preferably sulfate or hydrogen sulfate.
In one embodiment, the SCA is a particle with an average particle diameter of
from about
to about 500 microns. The term "average particle diameter" represents the mean
particle size
diameter of the actual particles of a given material. The mean is calculated
on a weight percent
basis. The mean is determined by conventional analytical techniques such as,
for example, laser
light diffraction or microscopic determination utilizing a light or scanning
electron microscope.
For typical manufacturing quality control, the Rotap screening method may be
used.
These and other conditioning agent containing amine ion-pair complexes are
described in
U.S. Patent Numbers 4,861,502, 5,073,274, 5,019,280, 4,857,213, and 4,913,828
to Debra S.
Caswell, et. al., and U.S. Patent No. 4,915,854, Mao, et. al.
In one embodiment, the ion-pair conditioning particles conditioning agent is
chosen from
preferred materials listed in U.S. Patent No. 5,019,280, at colunms 4 and 5.
A suitable source for ion-pair SCAs include prills of nominally 70% distearyl
amine + cumene
sulfonic acid ion pair and 30% bis (distearyl) ammonium sulfate from Degussa.
A preferred
composition for the SCA is shown below. The particle size by the Rotap method
is a median size
of about 95 microns, with less than from about 10% to about 25% less than
about 53 microns,
and less than from about 4% to about 6% greater than about 177 microns. The
level of SCA in
the compositions of the present invention is from about 1% to about 30%,
preferably from about
2% to about 15%.
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Structure of Distearyl Amine + Cumene Sulfonic Acid Ion Pair
and Bis (Distearyl) Ammonium Sulfate
CH3
Till
Rl HOSO ~ H
I CH3
R1 and R2 = Stearyl
70%: Distearyl Amine - Cumene Sulfonic Acid Ion - Pair
R2
1 o -2
Rl - N-H S04
H
2
R1 and R2 = Stearyl
30%: Bis (distearyl) Ammonium Sulfate (sulfate salt of above distearyl
protonated amine)
Other useful SCAs include alkyl and dialkyl imidazolines (both protonated and
unprotonated) such as, for example, Varisoft 445 Imidazoline (ex. Degussa),
polyethyleniniines
and ethoxylated polyethylenimines (preferred MW from about 2000 to about
25,000). Other
cationic polymers may function as antistatic agents, for example
Polyquaternium-6. While not
wishing to be bound by theory, cationic polymers can function as antistatic
agents added through
the wash if they are able to maintain at least some cationic charge in or
through the rinse cycle.
Still other antistatic agents include dialkyl and monoalkyl cationic
surfactants, and
combinations of monoalkyl cationic surfactant and fatty acids. Especially
preferred are tallow
trimethylammonium chloride, cocotrimethylammounium chloride,
oleyltrimethylammounium
chloride, and lauryltrimethylammonium chloride. Other examples are N,N-
di(tallowoyloxyethyl)-N,N-dimethylammonium chloride (available from Akzo under
the trade
name Armosoft DEQ), N,N-di(canola-oyloxyethyl)-N,N-dimethylammonium chloride
(available
from Degussa under the trade name Adogen CDMC), and di-(oleoyloxyethyl)-N,N-
methylhydroxyethylammonium methyl sulfate sold under the trade names Rewoquat
WE 15 and
Varisoft WE 16 , both available from Degussa. Other antistatic agents include
glycerol
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monostearate (Atmer 129 from Uniqema), Ethofat 245/25 (ethoxylated tall oil
from Akzo
Nobel), DC-5200 (lauryl PEG/PPG 18/18 methicone from Dow Corning), Ethomeen
18/12
(bis[2-hydroxyethyl]octadecylamine from Akzo Nobel), Ethomeen HT/12
(hydrogenated tallow
amine 2 EO from Akzo Nobel), and Wacker L656 aminofunctional silicone (from
Wacker
Chemical Corporation). These are generally less effective SCAs when added to
the wash cycle
that contains an anionic detergent compared to the distearyl amine + cumene
sulfonic acid ion
pair and bis (distearyl) ammonium sulfate prills. However, if the fabric
enhancer composition is
being formulated for a powder/liquid dual compartment unit dose pouch using
PVOH film, then
these and other effective SCAs can be used in powder or granular form in the
powder side of the
unit dose pouch. Effective SCAs are given in U.S. Patent Application
Publication No.
2005/0020476 Al, 9[9[15 - 74.
It has been discovered that for the best longer term stability of the ion pair
antistatic
agents, especially the distearyl amine/cumene sulfonic acid and distearyl
amine/sulfuric acid
prills, the level of anionic surfactant in an aqueous based composition (water
level at least about
50%) should be at least about 4%, preferably at least about 5%. While not
wishing to be bound
by theory, it appears that the higher levels of anionic surfactant can form a
coating around the
SCA particles and provide protection against an unfavorable interaction with
water such as
hydrolysis. This interaction with water can decrease the static control
performance when the
fabric enhancer compositions are stored at elevated temperatures for longer
periods of time, for
example, at 38 C.
It has also been discovered that for best stability at higher storage
temperatures (e.g., at
38 C) of distearyl amine/cumene sulfonic acid and distearyl amine/sulfuric
acid prills, the pH of
the fabric enhancer composition should be less than about 7, preferably from
about 3 to about 7,
more preferably from about 4 to about 6.
It has also been surprisingly found that perfumes may negatively interact with
the
distearyl amine/cumene sulfonic acid and distearyl amine/sulfuric acid prill,
with longer storage
times and higher temperatures in fabric enhancer compositions. While not
wishing to be bound
by theory, it is believed that perfume components (perfume raw materials) that
are hydrophobic
solublize and/or destroy the ion pair prill leading to eventual breakup of the
prill into smaller
pieces and eventually chemical reversion of the acid/base reaction that formed
the ion pair. This
perfume interaction with the ion pair can be solved in several ways. If the
fabric enhancer
composition is to be used in combination with a detergent product, for
example, in a dual pour,
dual compartment plastic bottle (an article where the fabric enhancer
composition and the
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detergent composition are dispensed at the same time but are physically
separated in one
container), then the perfume is added to the liquid detergent; and the SCA,
especially the distearyl
amine/cumene sulfonic acid and distearyl amine/sulfuric acid prills, is added
to the fabric
enhancer composition. Another solution is to formulate the SCA into the
detergent and the
perfume into the fabric enhancer composition. Thus, the perfume and SCA are
physically
separated in storage in the container and no interactions can occur. This same
method can be used
for unit dose packaging for the fabric enhancer composition with either water-
soluble or non-
water soluble film or even dual compartment plastic containers or trays. For
the water soluble
unit dose case with polyvinyl alcohol film (PVOH), a dual compartment pouch is
created by
vacuum forming and sealing the films. The SCA and the perfume are physically
separated since
the SCA is in the powder side of the pouch and the perfume is in the fabric
enhancer composition
in the liquid side of the pouch.
Another way to solve the stability issue is to form an article with two
compartments such
as a unit dose PVOH pouch. In this case, two liquid fills are used. On one
side, the liquid or gel
fabric enhancer composition containing the SCA, esp. the distearyl
amine/cumene sulfonic acid
and distearyl amine/sulfuric acid prills is added, but does not contain the
perfume in this case.
The perfume is added to the other compartment of the dual compartment pouch
either by itself or
as a mixture in a dispersing solvent. An example of a dispersing solvent is
dipropylene glycol or
other glycols or solvatropes or fatty alcohol ethoxylates or mixtures thereof.
The concentration of
perfume with dispersing solvent can be from about 5% to about 95% by weight of
perfume,
preferably from about 15 Io to about 75 Io perfume, and more preferably from
about 20 Io to about
50% perfume.
Even another way to solve the stability issue of perfume and SCA, especially
with the
distearyl amine/cumene sulfonic acid and distearyl amine/sulfuric acid prills,
is to use perfume
microcapsules instead of perfume oil. Perfume microcapsules are available from
several
suppliers such as Aveka (for example, a urea formaldehyde shell with a perfume
core). An
advantage for this approach is that perfume can effective be added to the
fabric enhancer
compositions containing the distearyl amine/cumene sulfonic acid and distearyl
amine/sulfuric
acid prills, and thus a simple, single compartment unit dose article can be
used. Also, a more
stable liquid fabric enhancer composition containing the SCA and with the
perfume in
microcapsules can be used in a standard plastic bottle or other container. In
one embodiment, the
perfume microcapsule is friable. In another embodiment, the perfume
microcapsule is moisture-
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31
activated. In another embodiment, the perfume microcapsule is heat-activated
(for example, by
the machine dryer).
H. Fabric Softenin2 A2ents
1. Diester Quaternary Ammonium (DEQA) Compounds
In one embodiment, the fabric care active is a fabric softening active
comprising a DEQA
compound. The DEQA compounds encompass a description of diamido fabric
softener actives
as well as fabric softener actives with mixed amido and ester linkages.
A first type of DEQA ("DEQA (1)") suitable as a fabric softening active in the
present
compositions includes compounds of the formula:
{R4-m - N+ - [(CH2)n - Y - R1]m} X-
wherein each R substituent is either hydrogen, a short chain C1-C6, preferably
C1-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the like, poly
(C2-3 alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; each
m is 2 or 3; each
n is from 1 to about 4, preferably 2; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)-,
or -C(O)-NR-
and it is acceptable for each Y to be the same or different; the sum of
carbons in each R1, plus
one when Y is -O-(O)C- or -NR-C(O) -, is C12-C22, preferably C14-C20, with
each R1 being a
hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R1 to be
unsaturated or
saturated and branched or linear and preferably it is linear; it is acceptable
for each R1 to be the
same or different and preferably these are the same; and X- can be any
softener-compatible anion,
preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate,
phosphate, and nitrate, more
preferably chloride or methyl sulfate. Preferred DEQA compounds are typically
made by
reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA
(triethanolamine) with
fatty acids. Some materials that typically result from such reactions include
N,N-di(acyl-
oxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyl-oxyethyl)-N,N-
methylhydroxyethylammonium methyl sulfate wherein the acyl group is derived
from animal fats,
unsaturated, and polyunsaturated, fatty acids, e.g., oleic acid, and/or
partially hydrogenated fatty
acids, derived from vegetable oils and/or partially hydrogenated vegetable
oils, such as, canola
oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall
oil, rice bran oil, etc. Non-
limiting examples of suitable fatty acids are listed in US 5,759,990 at column
4, lines 45-66.
Those skilled in the art will recognize that active softener materials made
from such process can
comprise a combination of mono-, di-, and tri-esters depending on the process
and the starting
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materials. Materials from this group preferred for the present invention
include those comprising
a high level of diester content; more than 40 Io, preferably more than 55 Io,
preferably more than
60%, still more preferably than 70%, and yet still more preferably at least
about 80% of the total
softener active weight (as used herein, the total softener active weight
includes the mass
encompassing all reaction products that comprise one or more R1 groups, the
percent softener
active as used herein to quantify the individual percentages of mono-, di-,
and tri-tail reaction
products refers to the ratio of an individual portion (mass) of the total
softener active wherein the
constituents contain a common number of R1 groups divided by the total
softener active weight
and multiplied by 100 to give a percentage of the total.) In one embodiment,
the diester content
comprises from about 55% to about 95% of the total percent of softener active
weight. Materials
from this group preferred for the present invention also include those
comprising a low level of
monoester content; preferably less than about 50%, preferably less than about
30%, more
preferably less than about 25%, and yet more preferably less than about 20%
monoester of the
total percent of softener active weight. In another embodiment, the monoester
content comprises
more than about 1 Io, preferably more than about 5 Io, more preferably than
about 10% of the total
percent of softener active weight. Non-limiting examples of preferred diester
quats for the
present invention include N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium
chloride
(available from Akzo under the trade name Armosoft DEQ) and N,N-di(canola-
oyloxyethyl)-
N,N-dimethylammonium chloride (available from Degussa under the trade name
Adogen
CDMC). Nonlimiting examples of available TEA ester quats suitable for the
present invention
include di-(hydrogenated tallowoyloxyethyl)-N,N-methylhydroxyethylammonium
methyl sulfate
and di-(oleoyloxyethyl)-N,N-methylhydroxyethylammonium methyl sulfate sold
under the trade
names Rewoquat WE 15 and Varisoft WE 16, both available from Degussa.
Additional preferred DEQA (1) actives include compounds comprising different Y
structures such as the those having the structure below where one Y = -C(O)-O-
and the other Y
_ -NH-C(O)-:
RI-C(O)O-R2 -N+(R4)n-R3-N(H)-C(O)-Ri X-
wherein n is 1 or 2; R' is a C6-C22, preferably a C8-C20, hydrocarbyl group or
substituted
hardrocarbyl groups that are branched or unbranched and saturated or
unsaturated; R 2 and R3 are
each Ci-Cs, preferably C2-C3, alkyl or alkylene groups; and R4 is H, or a Ci-
C3 alkyl or
hydroxyalkyl group. A non-limiting example of such softener is N-
tallowoyloxyethyl-N-
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tallowoylaminopropyl methyl amine. Additional non-limiting examples of such
softeners are
described in US 5,580,481 and US 5,476,597.
Other suitable fabric softening actives include reaction products of fatty
acids with
dialkylenetriamines in, e.g., a molecular ratio of about 2:1, said reaction
products containing
compounds of the formula:
R1-C(O~-NH-R2-NH-R3 NH-C(O~-R1
wherein R1, R2 are defined as above, and each R3 is a C1-6 alkylene group,
preferably an
ethylene group. Examples of these fabric softening actives are reaction
products of tallow acid,
canola acid, or oleic acids with diethylenetrianiine in a molecular ratio of
about 2:1, said reaction
product mixture containing N,N"-ditallowoyldiethylenetriamine, N,N"-dicanola-
oyldiethylenetriamine, or N,N"-dioleoyldiethylenetriamine, respectively, with
the formula:
R1-C(O)-NH-CH2CH2-NH-CH2CH2-NH-C(O)-R1
wherein R2 and R3 are divalent ethylene groups , R1 is defined above and an
acceptable
examples of this structure when R1 is the oleoyl group of a commercially
available oleic acid
derived from a vegetable or animal source, include Emersol 223LL or Emersol
7021,
available from Henkel Corporation.
Another fabric softening active for use in the present compositions has the
formula:
[R1-C(O~-NR-R2 N(R)2--R3 NR-C(O~-R1]+ X-
wherein R, R1, R2, R3 and X- are defined as above. Examples of this fabric
softening active are
the di-fatty amidoamines based softener having the formula:
[R1-C(O)-NH-CH2CH2-N(CH3)(CH2CH2OH)-CH2CH2-NH-C(O)-R1]+ CH3SO4-
wherein R1-C(O) is an oleoyl group, soft tallow group, or a hardened tallow
group available
commercially from Degussa under the trade names Varisoft 222LT, Varisoft
222, and
Varisoft 110, respectively.
A second type of DEQA ("DEQA (2)") compound suitable as a fabric softening
active in
the present compositions has the general formula:
[R3N+CH2CH(YR1)(CH2YR1)] X-
wherein each Y, R, R1, and X- have the same meanings as before. Such compounds
include
those having the formula:
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[CH3]3 N(+)[CH2CH(CH2O(O)CR1)O(O)CR1] C1(-)
wherein each R is a methyl or ethyl group and preferably each R 1 is in the
range of C 15 to C 19
As used herein, when the diester is specified, it can include the monoester
that is present. The
amount of monoester that can be present is the same as in DEQA (1).
These types of agents and general methods of making them are disclosed in U.S.
Pat. No.
4,137,180, Naik et al., issued Jan. 30, 1979. An example of a preferred DEQA
(2) is the "propyl"
ester quaternary ammonium fabric softener active having the formula 1,2-
di(acyloxy)-3-
trimethylammoniopropane chloride.
While it is acceptable to use fabric softening compounds with any transition
temperature;
preferably, for the present invention, the fabric softening compound has a
transition temperature
of equal to or less than about 50 C. It is acceptable for fabric softening
compounds to be made
with fatty acid precursors with a range of Iodine Values (herein referred to
as IV) from about zero
to about 140. One aspect of the invention provides for, but is not limited to,
performance
characteristics that include fabric softening composition and/or static
performance based upon IV
ranges. For example, in one embodiment the compositions of the present
invention comprises an
IV range of from at least about 40 to about 140; alternatively from at least
about 35 to about 65,
preferably from about 40 to about 60; alternatively from at least about 5 to
about 60, preferably
from about 15 to about 30, more preferably from about 15 to about 25.
Fabric softening compositions of the present invention that are clear
preferably contain
highly fluid fabric softening actives with transition temperatures less than
about 35 C. These
materials can be made with fatty acid precursors having high IV (greater than
about 50) or
comprising branching or other structural modifications leading to a low
transition temperature.
Additionally when unsaturated fabric softener actives are used for clear
compositions the
unsaturated moiety preferably has a cis:trans isomer ratio of at least 1:1,
preferably about 2:1,
more preferably about 3:1, and even more preferably 4:1 or higher. Some
preferred actives for
clear compositions are disclosed in US 6,369,025; U.S. Application Serial No.
09/554,969, filed
Nov. 24, 1998 by Frankenbach et al. (WO 99/27050); and US 6,486,121.
While it is acceptable for the present invention for the composition to
contain a number of
softening actives, including other fabric softening actives disclosed herein
below, the DEQA
fabric softening actives, and specifically those fabric softener actives with
two ester linkages, are
preferred fabric softening actives for the present invention.
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2. Other Fabric Softening Compounds
Instead of, or in addition to, the DEQA fabric softening actives described
hereinbefore,
the present compositions can also comprise a variety of other fabric softening
actives. These
other suitable fabric softening actives include:
(1) compounds having the formula:
[R4-m - N(+) - Rlm] A-
wherein each m is 2 or 3, each R1 is a C6-C22, preferably C14-C20, but no more
than one being
less than about C12 and then the other is at least about 16, hydrocarbyl, or
substituted
hydrocarbyl substituent, preferably C10-C20 alkyl or alkenyl (unsaturated
alkyl, including
polyunsaturated alkyl, also referred to sometimes as "alkylene"), most
preferably C12-C18 alkyl
or alkenyl, and branch or unbranched. While it is acceptable for the IV of the
parent fatty acid
containing the R1 group to range from zero to about 140, it is preferred for
the present invention
to have an IV of at least about 40. When the fabric softener composition will
be clear, it is
preferred for fabric softener active to be highly fluid by incorporating
branching in the
hydrocarbyl group by incorporating high unsaturation e.g. the IV of a fatty
acid containing this R1
group is from about 70 to about 140, more preferably from about 80 to about
130; and most
preferably from about 90 to about 115 (as used herein, the term "Iodine Value"
means the Iodine
Value of a"parent" fatty acid, or "corresponding" fatty acid, which is used to
define a level of
unsaturation for an R1 group that is the same as the level of unsaturation
that would be present in
a fatty acid containing the same R1 group) with, preferably, a cis/trans ratio
as specified above for
highly unsaturated compounds; each R is H or a short chain C1-C6, preferably
C1-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the like,
benzyl, or (R2 O)2-4H where each R2 is a C1-6 alkylene group; and A- is a
softener compatible
anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate,
phosphate, or nitrate;
more preferably chloride or methyl sulfate. Examples of these fabric softening
actives include
dialkydimethylammonium salts and dialkylenedimethylammonium salts such as
ditallowdimethylammonium chloride, dicanoladimethylammonium chloride, and
dicanoladimethylammonium methylsulfate. Examples of commercially available
dialkylenedimethylammonium salts usable in the present invention are di-
hydrogenated tallow
dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, and
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36
dioleyldimethylammonium chloride available from Degussa under the trade names
Adogen
442, Adogen 470, and Adogen 472, respectively.
(2) compounds having the formula:
// N CH2
RI C I A
O
11 \ N+ C H RI C G R2--' \
R
wherein each R, R1, and A- have the definitions given above; each R2 is a C1-6
alkylene group,
preferably an ethylene group; and G is an oxygen atom or an -NR- group.
Examples of this fabric
softening active are 1-methyl-1 -tallowylamidoethyl-2-oleylimidazolinium
methylsulfate and 1-
methyl-l-oleylamidoethyl-2-oleylimidazolinium methylsulfate wherein R1 is an
acyclic aliphatic
C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group, R5 is a
methyl group and
A- is a methyl sulfate anion, available commercially from Degussa under the
trade names
Varisoft 475 and Varisoft 3690, respectively.
(3) compounds having the formula:
N-CH2
RlC'
~ N-CH2
Ri-C-G-R~
wherein R1, R2 and G are defined as above. An example of this fabric softening
active is 1-
oleylamidoethyl-2-oleyliniidazoline wherein R1 is an acyclic aliphatic C15-C17
hydrocarbon
group, R2 is an ethylene group, and G is a NH group.
(4) reaction products of substantially unsaturated and/or branched chain
higher fatty
acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1, said
reaction products
containing compounds of the formula:
R1-C(O)-NH-R2-N(R3OH)-C(O)-R1
wherein R1, R2 and R3 are defined as above. Examples of this fabric softening
active are
reaction products of fatty acids such as tallow fatty acid, oleic fatty acid,
or canola fatty acid with
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N-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1, said
reaction product mixture
containing a compound of the formula:
R1-C(O)-NH-CH2CH2-N(CH2CH2OH)-C(O)-R1
wherein R1-C(O) is oleoyl, tallowyl, or canola-oyl group of a commercially
available fatty acid
derived from a vegetable or animal source. Nonlimiting examples of such
actives include
Emersol 223LL or Emersol 7021, which are derived from oleic acid and
available from
Henkel Corporation.
(5) compounds having the formula:
2+0
R R
N-R2-N
N~ N 2A0
R1 1
wherein R, R1, R2, and A- are defined as above.
Other compounds suitable as fabric softening actives herein are acyclic
quaternary
ammonium salts having the formula:
[Rl-N(R5)2-R6]+ A-
wherein R5 and R6 are C1-C4 alkyl or hydroxyalkyl groups, and R1 and A- are
defined as herein
above. Examples of these fabric softening actives are the
monoalkyltrimethylammonium salts
and the monoalkenyltrimethylammonium salts such as
monotallowyltrimethylammonium
chloride, monostearyltrimethylammonium chloride, monooleyltrimethylammonium
chloride, and
monocanolatrimethylammonium chloride. Commercial examples include
tallowtrimetylammonium chloride and soyatrimethylammonium chloride available
from Degussa
under the trade names Adogen 471 and Adogen 415.
(6) substituted imidazolinium salts having the formula:
O+
N-CH2
Rl-\ A~
N-CH2
R7/ \ H
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38
wherein R7 is hydrogen or a C1-C4 saturated alkyl or hydroxyalkyl group, and
R1 and A- are
defined as hereinabove;
(7) substituted imidazolinium salts having the formula:
N-CH2 O
R'C Ae
\
N-CH2
HO-R2 ~ R5
wherein R5 is a C1-C4 alkyl or hydroxyalkyl group, and R1, R2, and A- are as
defined above;
(8) alkylpyridinium salts having the formula:
R4_N O AO
wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon group and A- is an
anion. An example of
this fabric softening active is 1-ethyl-1 -(2-hydroxyethyl)-2-
isoheptadecylimidazolinium
ethylsulfate wherein R1 is a C17 hydrocarbon group, R2 is an ethylene group,
R5 is an ethyl
group, and A- is an ethylsulfate anion.
(9) alkanamide alkylene pyridinium salts having the formula:
O
RIC-NH-R2-N O AE)
wherein R1, R2 and A- are defined as herein above; and mixtures thereof.
Other suitable fabric softening actives for use in the present compositions
include
pentaerythritol compounds. Such compounds are disclosed in more detail in,
e.g., US 6,492,322
US 6,194,374; US 5,358,647; US 5,332,513; US 5,290,459; US 5,750,990, US
5,830,845 US
5,460,736 and US 5,126,060.
Polyquaternary ammonium compounds can also be useful as fabric softening
actives in
the present compositions and are described in more detail in the following
patent documents: EP
803,498; GB 808,265; GB 1,161,552; DE 4,203,489; EP 221,855; EP 503,155; EP
507,003; EP
803,498; FR 2,523,606; JP 84-273918; JP 2-011,545; US 3,079,436; US 4,418,054;
US
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39
4,721,512; US 4,728,337; US 4,906,413; US 5,194,667; US 5,235,082; US
5,670,472; Weirong
Miao, Wei Hou, Lie Chen, and Zongshi Li, Studies on Multifunctional Finishing
Agents, Riyong
Huaxue Gonye, No. 2, pp. 8-10, 1992; Yokagaku, Vol. 41, No. 4 (1992); and
Disinfection,
Sterilization, and Preservation, 4`h Edition, published 1991 by Lea & Febiger,
Chapter 13, pp.
226-30. The products formed by quaternization of reaction products of fatty
acid with N,N,N',N',
tetraakis(hydroxyethyl)-1,6-diaminohexane are also suitable for use in the
present invention.
Examples of ester and/or amide linked fabric softening actives useful in the
present
invention, especially for concentrated clear compositions, are disclosed in US
5,759,990 and US
5,747,443. Other fabric softening actives for clear liquid fabric softening
compositions are
described in US 6,323,172.
Examples of suitable amine softeners that can be used in the present invention
as fabric
softening actives are disclosed in US 6,630,441.Other fabric softening actives
that can be used
herein are disclosed, at least generically for the basic structures, in US
3,861,870; US 4,308,151;
US 3,886,075; US 4,233,164; US 4,401,578; US 3,974,076; and US 4,237,016.
Examples of
more biodegradable fabric softeners can be found in US 3,408,361; US
4,709,045; US 4,233,451;
US 4,127,489; US 3,689,424; US 4,128,485; US 4,161,604; US 4,189,593; and US
4,339,391.
The fabric softening active in the present compositions is preferably selected
from the
group consisting of ditallowoyloxyethyl dimethyl ammonium chloride,
dihydrogenated-
tallowoyloxyethyl dimethyl ammonium chloride, dicanola-oyloxyethyl dimethyl
ammonium
chloride, ditallow dimethyl ammonium chloride, tritallow methyl ammonium
chloride, methyl
bis(tallow amidoethyl)2-hydroxyethyl ammonium methyl sulfate, methyl
bis(hydrogenated tallow
amidoethyl)-2-hydroxyethyl ammonim methyl sulfate, methyl bis (oleyl
amidoethyl)-2-
hydroxyethyl ammonium methyl sulfate, ditallowoyloxyethyl dimethyl ammonium
methyl
sulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dicanola-
oyloxyethyl
dimethyl ammonium chloride, N-tallowoyloxyethyl-N-tallowoylaminopropyl methyl
amine, 1,2-
bis(hardened tallowoyloxy)-3-trimethylammonium propane chloride, and mixtures
thereof.
1. Solvents
Solvents are useful for fluidizing the fabric softening compositions of the
present
invention, and may provide good dispersibility, and in some embodiments,
provide a clear or
translucent composition. Suitable solvents of the present invention can be
water-soluble or
water-insoluble. Non-limiting examples include ethanol, propanol, isopropanol,
n-propanol, n-
butanol, t-butanol, propylene glycol, 1,3-propanediol, ethylene glycol,
diethylene glycol,
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dipropylene glycol, 1,2,3-propanetriol, propylene carbonate, phenylethyl
alcohol, 2-methyl 1,3-
propanediol, hexylene glycol, glycerol, sorbitol, polyethylene glycols, 1,2-
hexanediol, 1,2-
pentanediol, 1,2-butanediol, 1,4 butanediol, 1,4-cyclohexanedimethanol,
pinacol, 1,5-hexanediol,
1,6-hexanediol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol
(and ethoxylates),
2-ethyl-1,3-hexanediol, phenoxyethanol (and ethoxylates), glycol ethers such
as butyl carbitol and
dipropylene glycol n-butyl ether, ester solvents such as dimethyl esters of
adipic, glutaric, and
succinic acids, hydrocarbons such as decane and dodecane, or combinations
thereof. In one
embodiment, the composition is free or substantially free of one or more of
the above-identified
solvents.
Other examples of solvents include so called "principal solvents" preferably
having a
ClogP of from about -2.0 to about 2.6, more preferably from about -1.7 to
about 1.6, as defined
hereinafter, typically at a level that is less than about 80%, preferably from
about 10% to about
75%, more preferably from about 30% to about 70% by weight of the composition.
The
"calculated logP" (ClogP) is determined by the fragment approach of Hansch and
Leo (cf., A.
Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens,
J. B. Taylor
and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990. Principle solvents or
principal solvent
systems are described at U.S. Pat. Nos. 6,323,172; 6,369,025; and 5,747,443.
The level of
aqueous or aqueous plus solvent carrier may generally constitute the balance
of the present
compositions.
It will be recognized that solvents can be in solid form at room temperature
and are not
required to be liquids; for example, 1,4-cyclohexanedimethanol is a solid at
25 C. In addition,
surface active materials can be solvents, preferably nonionic or anionic
surfactants. Especially
preferred are alcohol ethoxylates. Additionally, free fatty acids, fatty acid
soaps, fatty
triglycerides, and fatty amines, amides, alcohols can also be solvents.
Especially preferred are
materials that are liquid at room temperature comprised of shorter chain
length, unsaturated,
and/or branched fatty acid moieties.
J. Thickeners and Structurants
Compositions of the present invention may contain a structurant or structuring
agent.
Structurants can also build viscosity to produce a preferred liquid gel
product form. Suitable
levels of this component are in the range from about 0% to 20%, preferably
from 0.1% to 10%,
and even more preferably from 0.1% to 3% by weight of the composition. The
structurant serves
to stabilize the silicone polymer in the inventive compositions and to prevent
it from coagulating
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and/or creaming. This is especially important when the inventive compositions
have fluid form,
as in the case of liquid or the gel-form fabric enhancer compositions.
Structurants suitable for use herein can be selected from thickening
stabilizers. These
include gums and other similar polysaccharides, for example gellan gum,
carrageenan gum,
xanthan gum, Diutan gum (ex. CP Kelco) and other known types of thickeners and
rheological
additives such as Rheovis CDP (ex. Ciba Specialty Chemicals), Alcogum L-520
(ex. Alco
Chemical), and Sepige1305 (ex. SEPPIC).
One preferred structurant is a crystalline, hydroxyl-containing stabilizing
agent, more
preferably still, a trihydroxystearin, hydrogenated oil or a derivative
thereof.
Without intending to be limited by theory, the crystalline, hydroxyl-
containing stabilizing
agent is a nonlimiting example of a "thread-like structuring system." "Thread-
like Structuring
System" as used herein means a system comprising one or more agents that are
capable of
providing a chemical network that reduces the tendency of materials with which
they are
combined to coalesce and/or phase split. Examples of the one or more agents
include crystalline,
hydroxyl-containing stabilizing agents and/or hydrogenated jojoba. Surfactants
are not included
within the definition of the thread-like structuring system. Without wishing
to be bound by
theory, it is believed that the thread-like structuring system forms a fibrous
or entangled
threadlike network in-situ on cooling of the matrix. The thread-like
structuring system has an
average aspect ratio of from 1.5:1, preferably from at least 10:1, to 200:1.
The thread-like structuring system can be made to have a viscosity of 0.002
m2/s (2,000
centistokes at 20 C) or less at an intermediate shear range (5 s-1 to 50 s-1)
which allows for the
pouring of the fabric enhancer composition out of a standard bottle, while the
low shear viscosity
of the product at 0.1 s-i can be at least 0.002 m~/s (2,000 centistokes at 20
C) but more preferably
greater than 0.02 m2/s (20,000 centistokes at 20 C). A process for the
preparation of a thread-
like structuring system is disclosed in WO 02/18528.
In one embodiment, cationic acrylic based homopolymers are utilized as
thickeners. One
such thickener is sold under the name Rheovis CDE by Ciba Specialty Chemicals
Corporation.
Other preferred stabilizers are uncharged, neutral polysaccharides, gums,
celluloses, and
polymers like polyvinyl alcohol, polyacrylamides, polyacrylates and co-
polymers, and the like.
K. Water
In one embodiment, the level of water in the fabric enhancer compositions is
relatively high,
for example at least about 50%, preferably at least about 60%, and more
preferably at least about
70% water. These are generally for packaging in a single compartment plastic
bottle or container,
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or in a dual compartment, dual pour plastic bottle or container combined with
another fabric care
composition, for example, a liquid detergent. In another embodiment the level
of water in highly
concentrated fabric enhancer compositions of the present invention is
generally low, less than
about 20% water, alternatively less than about 13%, alternatively less than
about 10%,
alternatively less than about 5%, alternatively even about zero, alternatively
from about 1% to
about 20%, by weight of the composition. Generally, some water is advantageous
from about 8%
to about 12% to prevent rigidity of a water soluble film, especially polyvinyl
alcohol films used
to encapsulate highly concentrated fabric enhancer compositions to form a unit
dose. High water
levels can cause the water soluble films used (for example, polyvinyl alcohol)
to encapsulate said
compositions of the present invention to leak or start to dissolve or
disintegrate prematurely,
either in the manufacturing process, during shipping/handling, or upon
storage. However, it has
been found that a low level of water can be desirable as medium for adding
water-soluble dyes to
the composition to give it an attractive color and to distinguish between
compositions with
different perfumes and /or added fabric care benefits. Oil soluble dyes can be
used without the
use of water medium but are not preferred since they can cause fabric staining
to occur. In one
embodiment a low level of water is needed to effectively hydrate a polymer
such as cationic guar
gum and/or a structuring agent in the context of a unit dose article with a
water soluble film.
L. Optional In2redients
The fabric enhancer compositions of the present invention may comprise one or
more
optional ingredients. In yet another embodiment, the composition is free or
substantially free of
one or more optional ingredients.
Fatty Acid
Fatty acid may be incorporated into fabric enhancer compositions as a
softening active. In
one embodiment, fatty acid may include those containing from about 12 to about
25, preferably
from about 13 to about 22, more preferably from about 16 to about 20, total
carbon atoms, with
the fatty moiety containing from about 10 to about 22, preferably from about
12 to about 18,
more preferably from about 14 (midcut) to about 18, carbon atoms. The fatty
acids of the present
invention may be derived from (1) an animal fat, and/or a partially
hydrogenated animal fat, such
as beef tallow, lard, etc.; (2) a vegetable oil, and/or a partially
hydrogenated vegetable oil such as
canola oil, safflower oil, peanut oil, sunflower oil, sesame seed oil,
rapeseed oil, cottonseed oil,
corn oil, soybean oil, tall oil, rice bran oil, palm oil, palm kernel oil,
coconut oil, other tropical
palm oils, linseed oil, tung oil, etc. ; (3) processed and/or bodied oils,
such as linseed oil or tung
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oil via thermal, pressure, alkali-isomerization and catalytic treatments; (4)
a mixture thereof, to
yield saturated (e.g. stearic acid), unsaturated (e.g. oleic acid),
polyunsaturated (linoleic acid),
branched (e.g. isostearic acid) or cyclic (e.g. saturated or unsaturated (x-
disubstituted cyclopentyl
or cyclohexyl derivatives of polyunsaturated acids) fatty acids. Non-limiting
examples of fatty
acids (FA) are listed in U.S. Pat. No. 5,759,990 at co14, lines 45-66.
Mixtures of fatty acids from different fat sources can be used, and in some
embodiments
preferred. Nonlimiting examples of FA's that can be blended, to form FA's of
this invention are
as follows:
Fatty Acyl Group FA1 FA2 FA3
C14 0 0 1
C16 3 11 25
C18 3 4 20
C14:1 0 0 0
C16:1 1 1 0
C18:1 79 27 45
C18:2 13 50 6
C18:3 1 7 0
Unknowns 0 0 3
Total 100 100 100
IV 99 125-138 56
cis/trans (C18:1) 5-6 Not Available 7
TPU 14 57 6
FA1 is a partially hydrogenated fatty acid prepared from canola oil, FA2 is a
fatty acid prepared
from soybean oil, and FA3 is a slightly hydrogenated tallow fatty acid.
It is preferred that at least a majority of the fatty acid that is present in
the fabric softening
composition of the present invention is unsaturated, e.g., from about 40% to
100%, preferably
from about 55% to about 99%, more preferably from about 60% to about 98%, by
weight of the
total weight of the fatty acid present in the composition, although fully
saturated and partially
saturated fatty acids can be used. As such, it is preferred that the total
level of polyunsaturated
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fatty acids (TPU) of the total fatty acid of the inventive composition is
preferably from about 0%
to about 75% by weight of the total weight of the fatty acid present in the
composition.
The cis/trans ratio for the unsaturated fatty acids may be important, with the
cis/trans ratio
(of the C18:1 material) being from at least about 1:1, preferably at least
about 3:1, more
preferably from about 4:1, and even more preferably from about 9:1 or higher.
The unsaturated fatty acids preferably have at least about 3%, e.g., from
about 3% to about
30% by weight, of total weight of polyunsaturates.
Typically, one would not want polyunsaturated groups in actives since these
groups tend to
be much more unstable than even monounsaturated groups. The presence of these
highly
unsaturated materials makes it desirable, and for the preferred higher levels
of polyunsaturation,
highly desirable, that the fatty acids of the present invention herein contain
antibacterial agents,
antioxidants, chelants, and/or reducing materials to protect from degradation.
While
polyunsaturation involving two double bonds (e.g., linoleic acid) is favored,
polyunsaturation of
three double bonds (linolenic acid) is not. It is preferred that the C18:3
level in the fatty acid be
less than about 3%, more preferably less than about 1%, and even more
preferably less than about
0.1 Io, by weight of the total weight of the fatty acid present in the
composition of the present
invention. In one embodiment, the fatty acid present in the composition is
essentially free,
preferably free of a C 18:3 level.
Branched fatty acids such as isostearic acid are preferred since they may be
more stable
with respect to oxidation and the resulting degradation of color and odor
quality.
The Iodine Value or "IV" measures the degree of unsaturation in the fatty
acid. In one
embodiment of the invention, the fatty acid has an IV preferably from about 40
to about 140,
more preferably from about 50 to about 120 and even more preferably from about
85 to about
105.
Clays
In one embodiment of the invention, the fabric care composition may comprise a
clay as a
fabric care active. In one embodiment clay can be a softener or co-softeners
with another
softening active, for example, silicone. Preferred clays include those
materials classified
geologically smectites and are described in U.S. Pat. Appl. Publ. 20030216274
Al, to Valerio
Del Duca, et al., published Nov. 20, 2003, paragraphs 107 - 120.
Other suitable clays are described U.S. Pat. Nos. 3,862,058; 3,948,790;
3,954,632;
4,062,647; and U.S. Patent Application Publication No. 20050020476A1 to Wahl,
et. al., page 5
and paragraph 0078 through page 6 and paragraph 0087.
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Perfume
The fabric enhancer compositions of the present invention can optionally
further comprise
perfume, typically at a level of from about 0.1% to about 10%, preferably from
about 1% to about
6%, and more preferably from about 1% to about 4%, by weight of the
composition. Preferably,
the perfume comprises enduring perfume ingredients that have a boiling point
of about 250 C or
higher and a ClogP of about 3.0 or higher, more preferably at a level of at
least about 25%, by
weight of the perfume. Suitable perfumes, perfume ingredients, and perfume
carriers are
described in US 5,500,138; and US 20020035053 Al
In one embodiment, the perfume comprises a perfume microcapsule. Suitable
perfume
microcapsules and perfume nanocapsules include: US 2003215417 Al; US
2003216488 Al; US
2003158344 Al; US 2003165692 Al; US 2004071742 Al; US 2004071746 Al; US
2004072719
Al; US 2004072720 Al; EP 1393706 Al; US 2003203829 Al; US 2003195133 Al; US
2004087477 Al; US 20040106536 Al; US 6645479; US 6200949; US 4882220; US
4917920;
US 4514461; US RE 32713; US 4234627. For purposes of the present invention,
the term
"perfume microcapsules" describes both perfume microcapsules and perfume
nanocapsules.
In yet another embodiment, the fabric enhancer composition of the present
invention
comprises odor control agents. Such agents include those described in
US5942217:
Uncomplexed cyclodextrin compositions for odor control", granted August 24,
1999. Other
agents suitable odor control agents include those described in the following:
US 5968404, US
5955093; US 6106738; US 5942217; and US 6033679.
In one embodiment, the fabric care benefit is dry fabric odor or fragrance to
fabric, and
the fabric care benefit agent is a perfume. The perfume can be delivered to
the wash via a unit
dose, such composition being contained in a water soluble film such as
polyvinyl alcohol.
Typically, the perfume is preferably mixed with a dispersing solvent, a
surfactant or mixture
thereof, but can be used alone. An example of a dispersing solvent is
dipropylene glycol or other
glycols or solvatropes or fatty alcohol ethoxylates or mixtures thereof. The
surfactant can be any
surfactant or emulsifying agent previously mentioned used at a non-detersive
level if
administered in a 64-65 liter basin of an automatic washing machine of water.
The concentration
of perfume in the dispersing solvent can be from about 5% to about 95%
perfume, preferably
from about 15% to about 75% perfume, and more preferably from about 20% to
about 50%
perfume. In forming a unit dose article, for example with PVOH film, the dose
of the perfume
containing composition is from about 0.1 ml to about 30 ml, alternatively from
about 0.5 ml to
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46
about 15 ml, alternatively from about 1 ml to about 5 ml. These can be in the
form of pouches,
envelopes, sachets, or round beads.
In another embodiment, the fabric care composition of the present invention is
free or
essentially free of other water insoluble fabric care benefit agents such as
silicones or other water
insoluble softening agents.
The fabric enhancer compositions can optionally further comprise a dye to
impart color to
the composition. Suitable dyes for the present fabric enhancer compositions
are FD&C Blue #1
and Liquitint colorants (ex. Milliken Chemical Company).
The fabric enhancer compositions of the present composition can optionally
further
comprise other ingredients selected from the group consisting of bodying
agents, drape and form
control agents, smoothness agents, wrinkle control agents, sanitization
agents, disinfecting
agents, germ control agents, mold control agents, mildew control agents,
antiviral agents, anti-
microbials, drying agents, stain resistance and repelling agents, soil release
agents, malodor
control agents, fabric refreshing agents, chlorine bleach odor control agents,
dye fixatives, dye
transfer inhibitors, color maintenance agents, optical brighteners, color
restoration/rejuvenation
agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, wear
resistance agents,
fabric integrity agents, anti-wear agents, defoamers and anti-foaniing agents,
rinse aids, UV
protection agents for fabrics and skin, sun fade inhibitors, insect
repellents, anti-allergenic agents,
enzymes, water proofing agents, fabric comfort agents, water conditioning
agents, shrinkage
resistance agents, stretch resistance agents, and mixtures thereof. A useful
enzyme for improving
the appearance and softness of cotton containing fabrics is a cellulase.
The fabric enhancer compositions of the present invention are preferably free
of effective
levels of detersive surfactants. Detersive surfactants, distinguished from the
surfactants that are
acting as emulsifiers or dispersing agents, are surfactants that are present
in a composition in an
amount effective to provide noticeable soil removal from fabrics. Typical
detersive surfactants
include anionic surfactants, such as alkyl sulfates and alkyl sulfonates, and
nonionic surfactants,
such as C8-C18 alcohols condensed with from 1 to 9 moles of C1-C4 alkylene
oxide per mole of
C8-C18 alcohol. Typical levels of surfactant in typical quality detergents are
from about 12% to
about 22%, and are used at a dosage in the range from about 90g to about 120g.
Preferred forms of the fabric enhancer composition of the present invention
are liquids
and gels. The fabric enhancer composition can also be in the form of a paste,
semi-solid,
suspension, powder, or any mixture thereof. A dual compartment article, for
example a dual
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47
compartment unit dose made form PVOH film, can be comprised of the same or 2
different
forms, for example a liquid/powder pouch, a liquid/liquid pouch, and a
gel/powder pouch.
The fabric enhancer compositions of the present invention, when added to a
rinse solution
of a laundering process, provide a concentration of at least about 10 ppm,
preferably at least
about 20ppm, preferably at least about 50 ppm, and more preferably from about
50 ppm to about
200 ppm, of fabric softening active (for example, silicone) and any optional
co-softening
compound in the wash solution. Applicants have found that these levels are
preferred to provide
an effective level to provide a noticeable softness benefit. Higher softener
active concentrations
could provide more softness, but could also possibly create staining or
spotting and unnecessary
cost. However, if for example, wrinkle control of fabrics is the primary
fabric care benefit,
higher softening active levels (for example, silicone) could be used.
The fabric enhancer compositions of the present invention can be added
directly, as-is, to
the wash cycle, preferably as a unit dose composition. It is preferred that
the film of the coating
material be water-soluble, preferably made of polyvinyl alcohol or a
derivative of polyvinyl
alcohol. Films comprised of hydroxypropyl methylcellulose and polyethylene
oxide may also be
used, as well as mixtures thereof, and mixtures with PVOH. Water-insoluble
films can also be
used, such as polyethylene and the like, for pouching.
When a fabric enhancer composition contained in a coating material comprising
a film is
desired, these materials may be obtained in a film or sheet form that may be
cut to a desired shape
or size. Specifically, it is preferred that films of polyvinyl alcohol,
hydroxypropyl methyl
cellulose, methyl cellulose, non-woven polyvinyl alcohols, PVP and gelatins or
mixtures be used
to encapsulate the fabric enhancer compositions. Polyvinyl alcohol films are
commercially
available from a number of sources including MonoSol LLC of Gary, Indiana,
Nippon Synthetic
Chemical Industry Co. Ltd. Of Osaka Japan, and Ranier Specialty Chemicals of
Yakima,
Washington. These films may be used in varying thicknesses ranging from about
20 to about 80
microns, preferably from about 25 to about 76 microns. For purposes of the
present invention, it
is preferred to use a film having a thickness of about 25 to about 76
micrometers for rapid
dissolution in a cold water wash. Where larger volumes of composition are to
be contained in
encapsulate, volumes exceeding about 25 ml, a thicker film may be desired to
provide additional
strength and integrity to the encapsulate. Further, it is preferred that the
water-soluble films be
printable and colored as desired.
Encapsulate articles such as pouches, pillows, sachets, beads, or envelopes
are easily
manufactured by heat-sealing multiple sheets together at their edges, leaving
an opening for
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48
inserting the fabric enhancer composition. This opening can then be heat-
sealed after the fabric
enhancer composition has been introduced. Pouches can also be made by vacuum
forming and
sealing. The size of the film segments used will depend on the volume of
composition to be
encapsulated. Heat sealing is described as one preferred method for forming
and sealing
encapsulated articles of the present invention, but it should be recognized
that the use of
adhesives, mechanical bonding, and partially solvating the films with water,
solvents, and
mixtures thereof, are alternative preferred methods for forming encapsulated
articles. One
suitable method for producing an article containing a composition of the
present invention is
thermoforming, preferably a water soluble film. The thermoforming process
consists of first
placing a sheet of film over a forming mold having at least one forming cavity
and heating the
film so that it forms into the recess of the cavity, placing a composition of
the present invention
into the formed cavity, and sealing a second sheet of film across the recess
to form the closed
article. Articles of multiple cavities may also be thermoformed in the same
manner with heat
applied to additional layers of film to make an additional recess for a second
compartment to
contain a composition of the present invention. Similar processes describing
related unit dose
articles can be found in US 6,281,183 B1, EP1126070, W00183668, W00183669,
W00185898,
W00183661, W00183657, W00183667, W00185892, W000208380, W00212432,
W00220361, W00240351, W000183658, W00240370, W00160966, W002060758,
W002060980, W002074893, W002057402, W003008513, W003008486, W003031266,
W003045812, W003045813, W002060757, EP1354939, EP1375351, EP1396440,
EP1431383,
EP1431384, EP1340692, W004085586. A unit dose article can also consist of the
enclosed
composition of the present invention shaped into a spherical bead as is
described in WO
97/35537.
During the manufacture of a unit dose with a film, for example PVOH, it is
useful to
leave an air bubble in the pouch of a liquid composition. The air bubble is
formed by slightly
under filling the liquid composition into the pouch as it is being formed, for
example, by vacuum.
This helps prevent the liquid composition from contacting the sealing area of
the film, for
example when a second film is placed over the first film that is holding the
liquid composition.
The air bubble is from about 0.1m1 to about lOml in volume, alternatively from
about 0.5m1 to
about 5m1. The air bubble also is a good aesthetic visual signal for the
consumer that the filled
pouch actually contains a liquid composition. As a visual signal, the bubble
should be from
about 1mm to about 20mm in diameter, alternatively from about 3mm to about
10mm.
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Plasticizers
For compositions intended to be enclosed or encapsulated by a film, especially
a highly
water-soluble film like polyvinyl alcohol, it is desirable to incorporate the
same or similar
plasticizers found in the film into the fabric softener composition. This
helps reduce or prevent
migration of the film plasticizers into the softener composition. Loss of
plasticizers from the film
can cause the article to become brittle and/or lose mechanical strength over
time. Typical
plasticizers to include in the highly concentrated fabric softener composition
are glycerin,
sorbitol, 1,2 propanediol, polyethylene glycols (PEGs), and other diols and
glycols and mixtures.
Compositions should contain from at least about 0.1%, preferably at least
about 1%, and more
preferably at least about 5% to about 70% plasticizer or mixture of
plasticizers.
In some embodiments, for example one contained in a water soluble film, it is
necessary
to choose solvents that do not compromise the physical integrity of the water
soluble film. Some
solvents act as plasticizers that will soften the film over time, others cause
the film to become
brittle over time by leaching out plasticizers from the water soluble film.
The ratio of the
plasticizing to non-plasticizing solvents in the formulation to be contained
in the water soluble
film must be balanced to uphold the physical integrity of the water soluble
film over time. For
example, one preferred mixture of solvents is polyethylene glycol (PEG) and
glycerin in a ratio
between about 4:3 to about 2:3 respectively, more preferably wherein the PEG
is PEG-400.
Another example is a mixture of three solvents, preferably polyethylene glycol
(PEG), glycerin,
and propylene glycol wherein the ratio of the PEG and glycerin is between
about 4:3 to about 2:3,
and the balance of the solvent composition of the formulation is made up of
propylene glycol.
The present invention can also include other compatible ingredients, including
those
disclosed U.S. Pat. Nos.: 5,686,376; 5,536,421.
Hueing Dyes and Brighteners.
In one embodiment, the fabric enhancer composition comprising a hueing dye. A
preferred hueing dye is one that exhibits a hueing efficiency of at least
about 20 and a wash
removal value in the range of from about 50% to about 98%. Suitable hueing
dyes are described
in the U.S. publication for pending U.S. Application Serial No. 11/244,774
(P&G Case 9795);
and U.S Pat. Publ. Nos.: 2005/0288207 Al; 2005/0287654 Al. Specific hueing
dyes may
include: Acid Violet 43 (Anthraquinone); Acid Violet 49 (Triphenylmethane);
Acid Blue 92
(Monoazo); Liquitint Violet DD; Liquitint Violet CT; and Liquitint Violet LS
(from Milliken
Chemical).
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In another embodiment, the fabric enhancer composition of the present
invention
comprises a brightener. Suitable brighteners, also called optical brighteners
or fluorescent
whitening agents (FWAs), are more fully described in the following: (1)
Ullman's Encyclopedia
of Industrial Chemistry, Fifth Edition, Vol. A18, Pages 153 to 176; (2) Kirk-
Othmer
Encyclopedia of Chemical Technology, Volume 11, Fourth Edition; and (3)
Fluorescent
Whitening Agents, Guest Editors R. Anliker and G. Muller, Georg Thieme
Publishers Stuttgart
(1975).
Chelating Agents
The compositions and processes herein can optionally employ one or more copper
and/or
nickel chelating agents ("chelators"). Such water-soluble chelating agents can
be selected from
the group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted
aromatic chelating agents and mixtures thereof, all as hereinafter defined.
The whiteness and/or
brightness of fabrics are substantially improved or restored by such chelating
agents and the
stability of the materials in the compositions are improved. The chelating
agents disclosed in
said U.S. Pat. No. 5,759,990 at column 26, line 29 through column 27, line 38
are suitable.
A wide variety of chelators can be used herein. Indeed, simple
polycarboxylates such as
citrate, oxydisuccinate, and the like, can also be used, although such
chelators are not as effective
as the amino carboxylates and phosphonates, on a weight basis.
Accordingly, usage levels may be adjusted to take into account differing
degrees of
chelating effectiveness. The chelators herein will preferably have a stability
constant (of the fully
ionized chelator) for copper ions of at least about 5, preferably at least
about 7, even more
preferably from about 15 to 25. Typically, the chelators will comprise from
about 0.1 Io to about
10%, more preferably from about 0.75% to about 5%, by weight of the
compositions herein, in
addition to those that are stabilizers. Preferred chelators include EDTA, DTPA
(diethylenetriaminepentaacetic acid), DETMP, DETPA, NTA, EDDS, TPED
(tetrahydroxypropyl
ethylenediamine), and mixtures thereof.
Dye Transfer Inhibition Agents
The compositions of the present invention may also include one or more dye
transfer inhibiting
agents. Suitable polymeric dye transfer inhibiting agents include, but are not
limited to,
polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone
and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or
mixtures thereof.
When present in the compositions herein, the dye transfer inhibiting agents
are present at levels
from about 0.0001 Io, more preferably about 0.01 Io, most preferably about
0.05 Io by weight of the
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51
cleaning compositions to about 10%, more preferably about 2%, most preferably
about 1 Io by
weight of the compositions.
Enzymes
Compositions of the present invention can comprise one or more of the
following enzymes:
Proteases like subtilisins from Bacillus [e.g. subtilis, lentus,
licheniformis, amyloliquefaciens
(BPN, BPN'), alcalophilus,] e.g. Esperase , Alcalase , Everlase and Savinase
(Novozymes),
BLAP and variants [Henkel]. Further proteases are described in EP130756,
W091/06637,
W095/10591 and W099/20726. Amylases ((x and/or (3) are described in WO
94/02597 and WO
96/23873. Commercial examples are Purafect Ox Am [Genencor] and Termamyl ,
Natalase ,
Ban , Fungamyl and Duramyl [all ex Novozymes]. Cellulases include bacterial
or fungal
cellulases, e.g. produced by Humicola insolens, particularly DSM 1800, e.g.
50Kda and "43kD
[Carezyme ]. Also suitable cellulases are the EGIII cellulases from
Trichoderma
longibrachiatum. Suitable lipases include those produced by Pseudomonas and
Chromobacter
groups. Preferred are e.g. LipolaseR, Lipolase UltraR, LipoprimeR and LipexR
from Novozymes.
Also suitable are cutinases [EC 3.1.1.50] and esterases. Carbohydrases e.g.
mannanase
(US6060299), pectate lyase (W099/27083) cyclomaltodextringlucanotransferase
(W096/33267)
xyloglucanase (W099/02663). Bleaching enzymes eventually with enhancers
include e.g.
peroxidases, laccases, oxygenases, (e.g. catechol 1,2 dioxygenase,
lipoxygenase (WO
95/26393), (non-heme) haloperoxidases .
It is common practice to modify wild-type enzymes via protein / genetic
engineering techniques
in order to optimize their performance in the detergent compositions. Enzymes
levels in
detergents in general are from 0.0001% to 2%, preferably 0.001% to 0.2%, more
preferably
0.005 Io to 0.1 Io pure enzyme (weight % of the composition ).
Enzymes Stabilizers
Enzymes can be stabilized using any known stabilizer system like calcium
and/or magnesium
compounds, boron compounds and substituted boric acids, aromatic borate
esters, peptides and
peptide derivatives, polyols, low molecular weight carboxylates, relatively
hydrophobic organic
compounds [e.g. certain esters, diakyl glycol ethers, alcohols or alcohol
alkoxylates], alkyl ether
carboxylate in addition to a calcium ion source, benzamidine hypochlorite,
lower aliphatic
alcohols and carboxylic acids, N,N-bis(carboxymethyl) serine salts;
(meth)acrylic acid-
(meth)acrylic acid ester copolymer and PEG; lignin compound, polyamide
oligomer, glycolic
acid or its salts; poly hexa methylene bi guanide or N,N-bis-3-amino-propyl-
dodecyl amine or
salt; and mixtures thereof.
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52
In liquid matrix, the degradation by the proteolytic enzyme of second enzymes
can be avoided by
protease reversible inhibitors [e.g. peptide or protein type, in particular
the modified subtilisin
inhibitor of family VI and the plasminostrepin; leupeptin, peptide
trifluoromethyl ketones,
peptide aldehydes.
Defoamers & Anti-foaming Agents
Compounds for reducing or suppressing the formation of suds in the wash or
rinse bath
solutions may also be unitized for use in the present invention. Suds
suppression can be of
particular importance in the so-called "high concentration cleaning process"
as described in U.S.
4,489,455 and 4,489,574 and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressers, and suds
suppressers are
well known to those skilled in the art. See, for example, Kirk Othmer
Encyclopedia of Chemical
Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc.,
1979). One
category of suds suppresser of particular interest encompasses monocarboxylic
fatty acid and
soluble salts therein, as described in U.S. Patent 2,954,347, issued September
27, 1960 to Wayne
St. John. The monocarboxylic fatty acids and salts thereof used as suds
suppressor typically have
hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable
salts include the alkali metal salts such as sodium, potassium, and lithium
salts, and ammonium
and alkanolammonium salts.
The compositions herein may also contain non-surfactant suds suppressers.
These
include, for example: high molecular weight hydrocarbons such as paraffin,
fatty acid esters
(e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aliphatic C 1 8-C40 ketones
(e.g., stearone), etc. Other suds inhibitors include N-alkylated amino
triazines such as tri- to
hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as
products of cyanuric
chloride with two or three moles of a primary or secondary amine containing 1
to 24 carbon
atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol
phosphate ester
and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate
esters. The
hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
The liquid
hydrocarbons will be liquid at room temperature and atmospheric pressure, and
will have a pour
point in the range of about -40 C and about 50 C, and a minimum boiling point
of not less than
about 110 C (atmospheric pressure). It is also known to utilize waxy
hydrocarbons, preferably
having a melting point below about 100 C. The hydrocarbons constitute a
preferred category of
suds suppresser for detergent compositions. Hydrocarbon suds suppressers are
described, for
example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The
hydrocarbons,
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53
thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or
unsaturated hydrocarbons
having from about 12 to about 70 carbon atoms. The term "paraffin," as used in
this suds
suppresser discussion, is intended to include mixtures of true paraffins and
cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressers comprises
silicone suds
suppressers. This category includes the use of polyorganosiloxane oils, such
as polydimethyl-
siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and
combinations of
polyorganosiloxane with silica particles wherein the polyorganosiloxane is
chemisorbed or fused
onto the silica. Silicone suds suppressers are well known in the art and are,
for example,
disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and
European Patent
Application No. 89307851.9, published February 7, 1990, by Starch, M. S. Other
silicone suds
suppressers are disclosed in U.S. Patent 3,455,839 which relates to
compositions and processes
for defoaming aqueous solutions by incorporating therein small amounts of
polydimethylsiloxane
fluids.
Mixtures of suds suppressers may also be used to advantage. Mixtures of
silicone and
silanated silica are described in German Patent Application DOS 2,124,526.
Silicone defoamers
and suds controlling agents in granular detergent compositions are disclosed
in U.S. Patent
3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al.
Another preferred foam
suppressant is a silicone/silicate mixture, e.g., Dow Corning's Antifoam AR.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount
of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,500 cs.
at 25 C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin
composed of (CH3)3Si01/2 units of Si02 units in a ratio of from (CH3)3 Si01/2
units and to Si02 units of from about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is
made up of certain polyethylene glycols or polyethylene-polypropylene glycol
copolymers or
mixtures thereof (preferred), or polypropylene glycol. The primary silicone
suds suppressor is
branched/cross linked and preferably not linear.
To illustrate this point further, typical liquid compositions with controlled
suds will
optionally comprise from about 0.001 to about 1, preferably from about 0.01 to
about 0.7, most
preferably from about 0.05 to about 0.5, weight % of said silicone suds
suppressor, which
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comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a
mixture of (a) a
polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing
silicone compound, (c)
a finely divided filler material, and (d) a catalyst to promote the reaction
of mixture components
(a), (b) and (c), to form silanolates; (2) at least one nonionic silicone
surfactant; and (3)
polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having
a solubility in
water at room temperature of more than about 2 weight %; and without
polypropylene glycol.
Similar amounts can be used in granular compositions, gels, etc, as described
in U.S. Patent Nos.
4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued
January 8, 1991,
5,288,431, Huber et al., issued February 22, 1994, and 4,639,489 and
4,749,740, Aizawa et al at.
A silicone suds suppressor particularly useful in the compositions and
articles of the
present invention comprises polyethylene glycol and a copolymer of
polyethylene
glycol/polypropylene glycol, all having an average molecular weight of less
than about 1,000,
preferably between about 100 and 800. The polyethylene glycol and
polyethylene/polypropylene
glycol copolymers herein have a solubility in water at room temperature of
more than about 2%,
and preferably more than about 5% by weight. The preferred solvent herein is
polyethylene
glycol having an average molecular weight of less than about 1,000, more
preferably between
about 100 and 800, most preferably between 200 and 400, and a copolymer of
polyethylene
glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight
ratio of
between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of
polyethylene
glycol:copolymer of polyethylene-polypropylene glycol.
Other suds suppressers useful herein comprise the secondary alcohols (e.g., 2-
alkyl
alkanols) and mixtures of such alcohols with silicone oils, such as the
silicones disclosed in U.S.
4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16
alkyl
alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which
is available from
Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are
available under the
trademark ISALCHEM 123 from Enichem. Mixed suds suppressers typically comprise
mixtures
of alcohol + silicone at a weight ratio of 1:5 to 5:1.
Rinse Aids
The fabric care actives of the present invention may also comprise rinse aids
which
typically comprise mixtures or one or more of the following fabric care
agents: anti-foaming
compounds, pH buffering agents, crystal growth inhibitors including carboxylic
compounds, and
organic diphosphonic and monophosphonic acids, heavy metal ion sequestrants
including
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chelants and chlorine scavengers, hydrophobic dispersants, polymeric
stabilizing agents, soil
release polymers, preservatives, and anti-microbials.
Ultraviolet Protection Ments
The incorporation of sunscreens and antioxidants into a wash or rinse bath
solution for
various benefits is also known in the art. For example, U.S. Patent No.
4,900,469, teaches
antioxidants in detergent solutions for bleach stability. Antioxidants have
likewise been used in
softeners and detergents to prevent fabric yellowing and to control malodor.
(See, JP 72/116,783,
Kao.) JP 63/162,798, teaches the use of sunscreens to stabilize the color of
fabric conditioning
compositions. U.S. Patent No. 5,134,223, Langer et al., issued July 28, 1992,
teaches copolymers
with a UV-absorbing monomer and a hydrophilic monomer to provide both anti-
fading and soil
release benefits. More specifically, this reference teaches the combination of
a polymer of UV-
absorbing monomers to a soil release polymer consisting of a hydrophilic group
(e.g. ethoxylate)
and hydrophobic group (e.g. terephthalate blocks). U.S. Patent No. 5,250,652,
Langer et al.,
issued Oct. 5, 1993, teaches copolymers containing at least one UVA light-
absorbing moiety
and/or one UVB light-absorbing moiety, one low molecular weight (i.e.,
monomeric) hydrophilic
moiety, and optionally one hydrophobic moiety for fabric care (detergents,
fabric softeners, etc.)
and skin care applications (cosmetics, shampoos, sunscreens, personal
cleansing compositions,
etc.). The use of low molecular weight hydrophilic moieties allows a loading
of UVA and/or
UVB moieties of up to about 95% and provides better dispersibility of the
polymer in an aqueous
media. The optional hydrophobic moiety provides control over the deposition of
the copolymer
on a desired surface.
Packaging
One aspect of the invention provides for a laundry article comprising: (a) a
container
comprising at least two compartments; (b) wherein at least in one compartment
comprises any
one composition of the present invention. In another embodiment, at least one
compartment
comprises a detersive surfactant composition. The term "detersive surfactant
composition" is
used herein the broadest sense to include any composition suitable to clean
fabric, preferably in a
washing machine. In yet another embodiment, the compartment comprising a
composition of the
present invention is different than the compartment comprising the detersive
surfactant
composition.
Any container comprising at least two compartments may be suitable. Non-
limiting
examples of such a container are described in include: U.S. Pat. No. 4,765514,
U.S. Pat. Appl.
Pub. Nos.:2002/0077265 Al; and 2002/0074347 Al.
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If the laundry article is a unit dose wherein the composition or compositions
are
encapsulated with a water soluble film (for example PVOH film), then the size
of the article is
from about 0.5g to about 90g, alternatively from about 5g to about 50g, and
preferable from about
lOg to about 40g.
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EXAMPLES
The following are non-limiting examples of the present invention.
Examples
INGREDIENTS I II III IV V
Fabric softening active a 18.985% 16.185% 14.239% 12.716% 12.716%
Cationic starch b 1.466% ---- 1.10% 0.97% 0.97%
Perfume 1.77% 1.77% 1.50% 1.3% 1.3%
Calcium chloride (25%) 0.598% 0.598% 0.598% 0.407% 0.407%
DTPA (37%) 0.02% 0.02% 0.02% 0.01% 0.01%
Preservative (1.5%) d 0.033% 0.033% 0.033% 0.022% 0.022%
Antifoam e 0.15% 0.15% 0.15% 0.10% 0.10%
Liquitint Blue Dyef 0.02% 0.02% 0.02% 0.01% 0.01%
Ammonium chloride (20%) 0.573% 0.573% 0.573% 0.390% 0.390%
Hydrochloric acid (25%) 0.032% 0.032% 0.032% 0.022% 0.022%
Silicone g 1.00% 2.00% 1.00% 1.00% 1.00%
Deposition Aid h 0.50% 0.50% 0.50% 0.50% 0.50%
Chelator' 0.50% 0.50% 0.50% ---- ----
Thickener' ---- 0.25% 0.25% 0.25% ----
Deionized water Balance Balance Balance 3alance Balance
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride at 86.5% active and
contains
ethanol solvent.
b Cationic starch based on common maize starch or potato starch, containing 25
Io to 95 Io
amylose and a degree of substitution of from 0.02 to 0.09, and having a
viscosity measured as
Water Fluidity having a value from 50 to 84. Example: CHA 501 from National
Starch.
Diethylenetriaminepentaacetic acid.
d KATHON CG available from Rohm and Haas Co.
e Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC23 10 at
10% active.
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T Available from Milliken Chemical Company
g 50% emulsion of 60,000 cSt PDMS available from Dow Coming.
h Polyethyleneimine, having an average molecular weight of -25,000, available
from BASF.
i Tetrahydroxypropyl ethylenediamine. Sold as Quadrol polyol from BASF.
jCationic acrylic homopolymer thickener available from Ciba.
All documents cited in the Detailed Description of the Invention are, are, in
relevant part,
incorporated herein by reference; the citation of any document is not to be
construed as an
admission that it is prior art with respect to the present invention.
It should be understood that every maximum numerical limitation given
throughout this
specification will include every lower numerical limitation, as if such lower
numerical limitations
were expressly written herein. Every minimum numerical limitation given
throughout this
specification will include every higher numerical limitation, as if such
higher numerical
limitations were expressly written herein. Every numerical range given
throughout this
specification will include every narrower numerical range that falls within
such broader
numerical range, as if such narrower numerical ranges were all expressly
written herein.
All parts, ratios, and percentages herein, in the Specification, Examples, and
Claims, are
by weight and all numerical limits are used with the normal degree of accuracy
afforded by the
art, unless otherwise specified.
While particular embodiments of the present invention have been illustrated
and
described, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
invention. It is
therefore intended to cover in the appended claims all such changes and
modifications that are
within the scope of this invention.
